Kirsten anchored the innings with solid 97 from 126 balls and hit eight fours to lead South Africa to victory on Wednesday over the world cup champions with 12 balls to spare.
Australia scored 240 for nine and South Africa replied with 241 for four, in 48 overs.
Opener Kirsten played a textbook innings, sharing partnerships of 129 with Jacques Kallis for the third wicket and 67 for the fourth with Jonty Rhodes.
Kallis scored 61 off 88 balls with five fours and a six, while Rhodes finished with 46 off 40 balls with two fours and two sixes.
But the man-of-the-match honour deservedly went to Kirsten, who hardly put a foot wrong before being bowled around his legs by a slower ball from Brett Lee in the 46th over.
Pollock's sudden elevation followed the sacking of Hansie Cronje after he admitted receiving money from bookmakers in return for information and forecasting on a one-day series with England and zimbabwe in January.
Pollock celebrated his new role by claiming the prized wicket of Mark Waugh, trapped in front without scoring, with his seventh ball of the match while wicket keeper Mark Boucher equalled a one-day international world record with five dismissals.
Boucher, who has dismissed five men once before, is among the 18 wicket keepers to have accomplished the feat a total of 26 times between them.
Four of his catches were off the bowling of paceman Makhaya Ntini. Australia were able to reach their respectable total largely through an eighth-wicket partnership of 65 between Damian Martyn and Damien Fleming which saw them recover from 120 for seven in the 27th over.
Fleming was caught off the bowling of fast bowler Jacques Kallis by Ntini at mid-on for 29 in the 42nd over, but Martyn was at the crease until the last ball of the innings when he was run out for 74. He faced 91 balls and hit seven fours.
Martyn also featured in an unbroken ninth-wicket stand of 55 with Brett Lee, who was dropped by Boucher off Pollock on 17 and went on to make 24 not out.
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