Medium pacer Pollock took two for 13 from 10 overs as Pakistan, who lost the toss and were put in to bat, were bundled out for 107 in 45.4 overs.
Wicketkeeper Mark Boucher took six catches, a record for dismissals in a one-day match for South Africa.
Boucher broke the record of five dismissals that he had held jointly with Jonty Rhodes and Dave Richardson.
The Pakistanis struggled to come to terms with the South African bowlers on a pitch that offered movement off the seam.
Captain Inzamam-ul-Haq ground out a gritty 45 not out, his team's top score in an innings in which just two of his team mates reached double figures.
Pakistan's first wicket fell without a run on the board when Imran Nazir edged the fourth ball of the match, which was bowled by Pollock, to Boucher.
The visitors slipped to six for two in the eighth over when Kamran Akmal was run out for three by Herschelle Gibbs's underarm throw after Younis Khan refused a single. Akmal fell down as he tried to scramble back to the non-striker's end.
Younis went for eight when his edged drive off Pollock was caught by Jacques Kallis at second slip.
That reduced Pakistan to 23 for three in the 13th over, and they were 41 for four when Mohammad Yousuf's budding innings was snuffed out for 21 when he tried to glide a delivery from medium pacer Andrew Hall to third man and edged to Boucher.
Inzamam and Shoaib Malik consolidated with a stand of 46 that would prove to be Pakistan's biggest partnership.
Medium pacer Justin Kemp ended the stand in the 33rd over when Malik, who scored 19, sparred at a leg-side delivery and was caught behind by Boucher.
Pakistan's remaining five wickets crashed for the addition of just 14 runs.
Inzamam faced 97 balls and hit four fours in his patient innings.
Pakistan 107 all out in 45.4 overs (Inzamam-ul-Haq 45 n o, Mohd Yousuf 21, Shoaib Malik 19; Pollock 2 for 13, Justin Kemp 2 for 9, Andre Hall 2 for 29, Ntini 1 for 20) Vs South Africa (yet to bat)