The pair both made 64 and wicket-keeper Geraint Jones also chipped in with 53 as England made the most of a decent batting track to acheive their highest total of the seven-match series they trail 4-1.
India could have been facing an even more daunting total had the visitors not lost their last six wickets in the final five overs as they looked to add quick runs.
Seamer Shanthakumaran Sreesanth was India's most successful bowler with 6-55, his maiden haul of five or more wickets in 13 one-day internationals. Four of his victims came late on in his second spell.
India, who had rushed to an unbeatable 4-0 win in the series, rested batsmen Virender Sehwag and Mohammad Kaif, and key off-spinner Harbhajan Singh. One match was abandoned due to rain.
Ashes hero Pietersen struck one six and 11 fours in his 55-ball knock and Collingwood two sixes and as many fours in his 84-ball innings.
England, put in to bat, were off to a solid start as stand-in captain Andrew Strauss (25) and Ian Bell (32) put on 43 for the opening wicket in less than 10 overs.
Left-handed Strauss led in the absence of Andrew Flintoff, who was rested for the second successive game.
Pietersen then put his team on course for a big total with his aggressive eighth half-century in one-dayers.
He put on 63 for the third wicket with Bell and 55 for the next with Collingwood before slog-sweeping spinner Yuvraj Singh straight down the throat of debutant Robin Uthappa at deep mid-wicket.
Jones and Collingwood then maintained the impressive run-rate as they put on 92 for the fifth wicket off 14 overs.
Collingwood reached his 10th half-century in style, hitting off-spinner Ramesh Powar for a six over mid-wicket and then lofting over long-on for another six in the same over.
Jones fell immediately after completing his fourth half-century, caught behind off Sreesanth.