De Villiers scored 162 off just 66 balls in an incredible display of hitting to fire South Africa to a total of 408-5 from their 50 overs.
His hundred came off 52 deliveries, making that the second-fastest in World Cup history, behind Kevin O???Brien???s 50-ball effort for Ireland against England in 2011.
Chris Gayle could not repeat his double-hundred heroics following his 215 in the West Indies??? last game against Zimbabwe ??? he fell for three ??? as the West Indies crumbled to 151 all out with Imran Tahir taking a career-best 5-45.
South Africa won the toss and chose to bat first at the SCG but opener Quinton de Kock fell cheaply again for 12 as he picked out the man at cover off Jason Holder.
Hashim Amla (65) and Francois du Plessis (62) passed fifty as they rebuilt the innings with a 127-run partnership but both fell within two balls of each other in the 30th over to Chris Gayle.
That left the Proteas 146-3 when De Villiers came to the crease before his astonishing innings saw 261 runs come from the final 20 overs, including 72 from the batting powerplay and 150 from the final 10.
Rilee Rossouw???s 61 from 39 balls added to the carnage before he departed with eight overs to go ??? getting a thick edge off Andre Russell through to Denesh Ramdin ??? and David Miller (20 off 16) fell to an incredible one-handed catch on the boundary by Jason Taylor.
But in truth, the show was at the other end as De Villiers ??? despite seemingly suffering from heat exhaustion and cramp ??? first went through to his hundred with a six off Holder in the 48th over and then reached his 150 in the same fashion, off the same bowler, a mere 12 balls later.
Holder???s final two overs cost him 64 as he finished with figures of 1-104, despite having only conceded nine runs in his first five overs.
It helped propel South Africa to the second-highest score ever in a World Cup, leaving the West Indies a mammoth 409 runs to win.
If there was ever a man capable of such a task it would be Gayle, fresh of a World Cup double-hundred, but he lasted only four balls ??? clean bowled by Kyle Abbott in the second over.
Marlon Samuels ??? who also scored a century in their win over Zimbabwe ??? fell for a nine-ball duck to Abbott two overs later and with him went any super slim hope of a West Indies win.
Jonathan Carter was the next to go, for 10, mis-timing a pull shot off Morne Morkel to that man De Villiers at mid-on. It was the first of five wickets to fall for 11 runs as Tahir ripped through the West Indies middle-order, leaving them 63-7 and in danger of a record ODI defeat.
Their captain, Holder, helped them avoid that embarrassment top-scoring with 56 off 48 balls but it was the only bright spark in an otherwise disastrous outing for the men from the Caribbean.
Dale Steyn eventually picked up his wicket ??? only his third so far of the World Cup ??? before Morkel picked up the final wicket of Sulieman Benn three balls later with 16.5 overs to spare.