De Villiers struck eight fours and two sixes in a classy 10th one-day century.
He shared 119 with Graeme Smith (45) and an unbroken 84 with JP Duminy (42) as South Africa side eased to victory with 43 deliveries left in New Delhi.
West Indies were all out for 222 with 15 balls unused, Darren Bravo hitting a six in his promising 73, and debutant leg-spinner Imran Tahir taking 4-21.
It was a magnificent innings from De Villiers, full of classical strokeplay, and underlined why South Africa are considered one of the strong favourites for the tournament.
Despite having consistently strong squads the South Africans have yet to reach a final but will have alerted all of their rivals with the quality of their performance.
However, it was not their fearsome pace pairing of Dale Steyn and Morne Morkel that did the early damage with the ball in this match.
After inviting West Indies to bat they sprung a surprise by opening with spinner Johan Botha in a bid to combat the kind of power hitting from Chris Gayle that brought 92 from 40 balls in the Big Bash, Australia's domestic Twenty20 competition, in January.
There was always the fear that the early demise of Gayle would leave an anti-climactic air, and he was caught low at slip from the third ball of the match.
But 22-year-old Bravo, five years younger than half-brother Dwayne, evoked shades of Gayle and distinct memories of Brian Lara with some stylish, calypso-style shots.
He struck two fours in Jacques Kallis' first over and wristily made his way to his third one-day international fifty in only his 14th match, hitting Tahir with one hand off the bat for a six that sailed over long-on.
The hundred partnership with Devon Smith came up in 117 balls with Bravo contributing 67 but he played across one from Botha and was lbw. The Windies risked a referral on their new hero but replays did not show anything to change the verdict.
Pakistan-born Tahir, who qualified to play for South Africa on 1 January, then deceived Smith in the flight to earn a routine caught and bowled, kissing the team's badge in jubilation before trapping Ramnaresh Sarwan lbw pushing forward in his next over.
Bravo senior survived a fairly straightforward return catch to Tahir on one which would have made it 122-5, but looked set to emulate his sibling's half century after thumping three legside sixes in an exciting attacking rearguard, before the Windies pressed the self-destruct button again.
Chanderpaul reverse swept behind square straight to short fine-leg but called for a suicidal single, and there was no need for the third umpire as an enraged Bravo, who was later carried off in agony after jarring his knee in his follow-through whilst bowling, was run out for 40 from 37 balls.
Dangerman Kieron Pollard arrived to considerable acclaim from the crowd following his Twenty20 exploits in guiding Mumbai to the final of the 2010 Indian Premier League.
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But Steyn beat him for pace lbw first ball following a referral, after the original appeal was rejected, and quickly polished off the tail to finish with 3-24 as the final five wickets fell for 13.
Under the floodlights West Indies also opened with spin and, after the solitary paceman Kemar Roach had the top-ranked ODI batsman Hashim Amla superbly caught by wicketkeeper Devon Thomas at full stretch off the inside edge, giant slow left-armer Sulieman Benn turned one away to take the edge of the prolific Kallis, and was taken low at slip.
I'm very chuffed with the way we have started, there is a good vibe amongst the group
SA captain Graeme Smith
De Villiers eased the pressure with a succession of exquisitely timed strokes, particularly through the off-side, ably supported by his captain, who was rather less easy on the eye but effective as always.
The 27-year-old, a scratch golfer and talented hockey player, danced down the wicket to whip Gayle over long-on for six to bring up his fifty from 54 balls and the team hundred off the final ball of the 22nd over.
The century partnership, the seventh between the pair in ODIs, came from 118 balls, De Villiers unsurprisingly the dominant scorer with 60 as the West Indies bowling attack looked painfully threadbare.
Using his quick feet and hand-eye co-ordination to great effect, De Villiers dispatched Benn many rows back at long-off but with 84 needed he lost Smith, who played an ugly heave at Pollard and was bowled through the gate.
Rain fell briefly but fittingly play resumed and De Villiers reached three figures from 97 balls, notching South Africa's fastest World Cup century, to secure victory with the composed Duminy.
It was South Africa's 12th successive win over the Windies, who are now below Bangladesh a lowly ninth in the ICC rankings.
Skipper Smith, whose team now have to wait until 3 March before their next match against the Netherlands, said: "I'm very chuffed with the way we have started, there is a good vibe amongst the group.
"AB played incredibly well, I think those things come with experience, to read situations. And this was one of those times. He played superbly well on a wicket that wasn't so free-scoring. It was an incredible knock to go faster than a run-a-ball and he controlled the game superbly for us."
Such a stylish century was always going to deny Tahir the Man-of-the-Match award and De Villiers quipped: "It's a batsman's game! but it's amazing to see how composed and calm he was for a debutant in a World Cup game so big ups to him and we'll definitely be sharing a drink. He can have half the award!"
"I'm very, very happy with the way I batted, I have not been timing it that well in the nets so it was good it came right when it mattered."
Windies skipper Darren Sammy said: "We had an opportunity to get a lot more runs. There were a few positives, Darren Bravo played really well and we hope he can continue like this. But we kept losing wickets and it did not help."
MATCH SCORECARD
He shared 119 with Graeme Smith (45) and an unbroken 84 with JP Duminy (42) as South Africa side eased to victory with 43 deliveries left in New Delhi.
West Indies were all out for 222 with 15 balls unused, Darren Bravo hitting a six in his promising 73, and debutant leg-spinner Imran Tahir taking 4-21.
It was a magnificent innings from De Villiers, full of classical strokeplay, and underlined why South Africa are considered one of the strong favourites for the tournament.
Despite having consistently strong squads the South Africans have yet to reach a final but will have alerted all of their rivals with the quality of their performance.
However, it was not their fearsome pace pairing of Dale Steyn and Morne Morkel that did the early damage with the ball in this match.
After inviting West Indies to bat they sprung a surprise by opening with spinner Johan Botha in a bid to combat the kind of power hitting from Chris Gayle that brought 92 from 40 balls in the Big Bash, Australia's domestic Twenty20 competition, in January.
There was always the fear that the early demise of Gayle would leave an anti-climactic air, and he was caught low at slip from the third ball of the match.
But 22-year-old Bravo, five years younger than half-brother Dwayne, evoked shades of Gayle and distinct memories of Brian Lara with some stylish, calypso-style shots.
He struck two fours in Jacques Kallis' first over and wristily made his way to his third one-day international fifty in only his 14th match, hitting Tahir with one hand off the bat for a six that sailed over long-on.
The hundred partnership with Devon Smith came up in 117 balls with Bravo contributing 67 but he played across one from Botha and was lbw. The Windies risked a referral on their new hero but replays did not show anything to change the verdict.
Pakistan-born Tahir, who qualified to play for South Africa on 1 January, then deceived Smith in the flight to earn a routine caught and bowled, kissing the team's badge in jubilation before trapping Ramnaresh Sarwan lbw pushing forward in his next over.
Bravo senior survived a fairly straightforward return catch to Tahir on one which would have made it 122-5, but looked set to emulate his sibling's half century after thumping three legside sixes in an exciting attacking rearguard, before the Windies pressed the self-destruct button again.
Chanderpaul reverse swept behind square straight to short fine-leg but called for a suicidal single, and there was no need for the third umpire as an enraged Bravo, who was later carried off in agony after jarring his knee in his follow-through whilst bowling, was run out for 40 from 37 balls.
Dangerman Kieron Pollard arrived to considerable acclaim from the crowd following his Twenty20 exploits in guiding Mumbai to the final of the 2010 Indian Premier League.
But Steyn beat him for pace lbw first ball following a referral, after the original appeal was rejected, and quickly polished off the tail to finish with 3-24 as the final five wickets fell for 13.
Under the floodlights West Indies also opened with spin and, after the solitary paceman Kemar Roach had the top-ranked ODI batsman Hashim Amla superbly caught by wicketkeeper Devon Thomas at full stretch off the inside edge, giant slow left-armer Sulieman Benn turned one away to take the edge of the prolific Kallis, and was taken low at slip.
I'm very chuffed with the way we have started, there is a good vibe amongst the group
SA captain Graeme Smith
De Villiers eased the pressure with a succession of exquisitely timed strokes, particularly through the off-side, ably supported by his captain, who was rather less easy on the eye but effective as always.
The 27-year-old, a scratch golfer and talented hockey player, danced down the wicket to whip Gayle over long-on for six to bring up his fifty from 54 balls and the team hundred off the final ball of the 22nd over.
The century partnership, the seventh between the pair in ODIs, came from 118 balls, De Villiers unsurprisingly the dominant scorer with 60 as the West Indies bowling attack looked painfully threadbare.
Using his quick feet and hand-eye co-ordination to great effect, De Villiers dispatched Benn many rows back at long-off but with 84 needed he lost Smith, who played an ugly heave at Pollard and was bowled through the gate.
Rain fell briefly but fittingly play resumed and De Villiers reached three figures from 97 balls, notching South Africa's fastest World Cup century, to secure victory with the composed Duminy.
It was South Africa's 12th successive win over the Windies, who are now below Bangladesh a lowly ninth in the ICC rankings.
Skipper Smith, whose team now have to wait until 3 March before their next match against the Netherlands, said: "I'm very chuffed with the way we have started, there is a good vibe amongst the group.
"AB played incredibly well, I think those things come with experience, to read situations. And this was one of those times. He played superbly well on a wicket that wasn't so free-scoring. It was an incredible knock to go faster than a run-a-ball and he controlled the game superbly for us."
Such a stylish century was always going to deny Tahir the Man-of-the-Match award and De Villiers quipped: "It's a batsman's game! but it's amazing to see how composed and calm he was for a debutant in a World Cup game so big ups to him and we'll definitely be sharing a drink. He can have half the award!"
"I'm very, very happy with the way I batted, I have not been timing it that well in the nets so it was good it came right when it mattered."
Windies skipper Darren Sammy said: "We had an opportunity to get a lot more runs. There were a few positives, Darren Bravo played really well and we hope he can continue like this. But we kept losing wickets and it did not help."
MATCH SCORECARD
