Amla hit 122 with De Villiers eclipsing him on 128 as they managed 238 as a pairing before the hosts finished on 343 for five after being sent in.
South Africa struggled early on, with left-arm fast bowler Mohammad Irfan taking two early wickets as Pakistan's fast bowlers exploited some early life in the pitch.
The first two overs, by Junaid Khan and Irfan, were maidens before Irfan bowled Graeme Smith with the total on four.
Amla and Colin Ingram put on 38 for the second wicket but the stand took 65 balls before Irfan produced a vicious lifter which Ingram could only fend to wicketkeeper Kamran Akmal.
However, the momentum swung when De Villiers joined Amla at the crease.
Their record stand beat by one run the previous one-day international third wicket mark set by Rahul Dravid and Sachin Tendulkar for India against Kenya in 1999.
That ensured Pakistan would have a challenging run chase on a ground renowned for high scoring.
De Villiers was quickly into his stride and the pair posted a fifty partnership off just 38 balls.
The rate slowed slightly when Pakistan brought their spin bowlers into action and after 35 overs South Africa were on 115 but that was when the torrent began as the last 15 overs yielded 156 runs.
Amla reached his 11th one-day international century off 99 balls, while De Villiers earned his 14th century in the format off 87 deliveries.
Amla was caught at cover for 122 off 113 balls with nine fours and a six and De Villiers was held at deep midwicket for 128 off 108 deliveries, with 12 fours and three sixes.
Pakistan were briefly reduced to ten men after Irfan, who had been a doubtful starter because of a hamstring strain, left the field for treatment.
He was replaced by Umar Akmal but after 20 minutes the umpires informed Pakistan captain Misbah-ul-Haq that the maximum 20 minutes allowed for treatment had expired. Pakistan had a fielder short for two overs before Irfan returned.
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