First Test, Perth (day five): South Africa 281 & 414-4 beat Australia 375 & 319 by six wickets Match scorecard
De Villiers shared century partnerships with both Kallis and Duminy
South Africa completed the second-highest successful run chase in Test history as they made 414-4 to beat Australia in the first Test in Perth.
The tourists began the final day on 227-3, with Jacques Kallis (57) and AB de Villiers at the crease.
Mitchell Johnson removed Kallis - his 11th wicket of the match - at 303-4.
But de Villiers made a sparkling 106 not out, adding 111 for the fifth wicket with debutant JP Duminy (50 not out) as the Proteas cruised home.
The all-time record Test run chase was West Indies' 418-7 against Australia in Antigua in 2003.
HIGHEST SUCCESSFUL TEST CHASES
418-7 West Indies v Australia, Antigua, May 2003
414-4 South Africa v Australia, Perth, Dec 2008
406-4 India v West Indies, Trinidad, Apr 1976
404-3 Australia v England, Headingley, Jul 1948
387-4 India v England, Chennai, Dec 2008
Captain Graeme Smith had laid the foundations for South Africa's victory with his 108 on day four, but he and Hashim Amla (53) had both fallen to Johnson to keep the game in the balance.
Kallis and De Villiers extended their partnership to 124 - with Kallis taking the lead role - before Kallis was caught by Mike Hussey at point soon after Australia had taken the second new ball.
At that stage, the tourists still needed another 111 runs to win with six wickets remaining - giving the Aussies renewed hope of victory.
But although left-arm seamer Johnson sent down more than 34 overs for his 3-98, for match figures of 11-159, Ricky Ponting's side were unable to make another breakthrough.
De Villiers took 179 balls to reach his carefully-compiled hundred, while left-hander Duminy put his first-innings failure behind him to provide the perfect supporting role.
"JP and I have played cricket together from a very young age, we understand each other's games and it just paid off today," de Villiers said after picking up the man-of-the-match award.
Duminy, 24, completed a debut to remember by hitting the winning runs - a three through cover - to reach his half century.
By contrast, Australia's bowling attack looked a shadow of its former self - with Johnson having taken 11 of the 14 South African wickets to fall during the game.
An out-of-sorts Brett Lee finished with match figures of 1-132, while rookie off-spinner Jason Krejza has now conceded more than 100 runs in each of the four Test innings in which he has bowled.
It is the first time Australia has lost the first Test of a home series since their defeat by West Indies in Brisbane in November 1988.
The three-match Test series continues with the traditional Boxing Day Test at Melbourne on 26 December.
The world's three leading news agencies are not covering the series due to a dispute with Cricket Australia.
Reuters, Agence France-Presse and Associated Press have suspended all coverage of the 2008-09 season.
Their photographers and reporters did not supply material from within the ground. As a result, we cannot use pictures from the current match.