England slipped to 45 for two but Collingwood led the recovery with his fifth ODI century, off 108 deliveries with seven fours and two sixes.
Opener Jonathan Trott, continuing his excellent start to the tour, also played with calm assurance as he hit 87 off 119 balls with eight fours.
Collingwood, who surpassed Alec Stewart (170) as England’s most-capped ODI player, and Trott put on 162 for the third wicket off 189 deliveries.
“It was a very proud day to be able to celebrate the record like that,” Collingwood told reporters. “Everything went pretty much perfectly both as an individual and a team.
“It’s not far off one of my best innings for England, the way it turned out was special. I enjoyed the whole innings.”
Earlier, South Africa made 250 for nine after being put in to bat on a slow pitch that offered early assistance to the seamers. The highest partnership for the hosts was between opening batsman Hashim Amla (57), coming into the side in place of the injured Jacques Kallis, and JP Duminy (41) when they put on 73 for the third wicket.
Alviro Petersen also struck 64 in 65 balls going in at number five.
DIVING CATCH
Collingwood started his day well by taking a wonderful diving catch at backward point to dismiss AB de Villiers for two off paceman James Anderson.
The former captain also bowled his medium-pacers to good effect to remove Amla and the dangerous Albie Morkel (6). Trott’s medium-pace was effective as he conceded just 21 runs in seven overs while Anderson claimed three for 60 as several South Africans played themselves in before giving their wickets away.
“Paul Collingwood is one of those cricketers you’d like to have in your side because he always gives 100 percent and has good character,” said home captain Graeme Smith.
“It’s a credit to him that he’s now England’s most-capped player, we as a team congratulate him. He played superbly well today, the way he marshalled the innings.”
The third match is in Cape Town on Friday.
Scoreboard
South Africa innings
H. Amla c Strauss b Collingwood 57
G. Smith c Strauss b Bresnan 12
A. de Villiers c Collingwood b Anderson 2
J-P. Duminy c Prior b Wright 41
A. Petersen b Bresnan 64
R. McLaren c Prior b Anderson 5
A. Morkel c Morgan b Collingwood 6
M. Boucher not out 30
R. van der Merwe c Bresnan b Anderson 5
D. Steyn c Trott b Mahmood 12
C. Langeveldt not out 6
Extras (lb-3, w-6, nb-1) 10
Total (nine wickets; 50 overs) 250
Fall of wickets: 1-27 2-38 3-111 4-131 5-155 6-165 7-205 8-222 9-242.
Bowling: Anderson 10-0-60-3 (2w), Bresnan 10-0-46-2 (2w), Mahmood 7-0-41-1 (2w, 1nb), Wright 7-0-28-1, Rashid 3-0-27-0, Collingwood 6-0-24-2, Trott 7-0-21-0.
England innings
J. Trott c Amla b Langeveldt 87
A. Strauss c De Villiers b Langeveldt 16
K. Pietersen b Morkel 4
P. Collingwood not out 105
E. Morgan not out 27
Extras (lb-1, w-8, nb-4) 13
Total (three wickets; 46 overs) 252
Fall of wickets: 1-28 2-45 3-207.
Did not bat: M. Prior, L. Wright, A. Rashid, T. Bresnan, S. Mahmood, J. Anderson.
Bowling: Steyn 10-0-64-0 (1nb), Langeveldt 10-0-46-2 (1nb), McLaren 8-0-43-0 (3w, 1nb), Morkel 5-0-26-1 (1w, 1nb), Van der Merwe 9-0-55-0 (4w), Duminy 4-0-17-0.
First ODI – Match abandoned without a ball bowled
Second ODI – England beat South Africa by seven wickets
Third ODI – Cape Town, Nov. 27
Fourth ODI – Port Elizabeth, Nov. 29
Fifth ODI – Durban, Dec. 4