Pietersen smashed a 94-ball 110 before retiring hurt to let his colleagues get some batting practice as England reached a strong 408 for three on day one of the game.
Left-handed Cook, who did not play against Mumbai A, yet again batted splendidly but missed out on his century by three runs after electing to bat.
Ian Bell (57) and Samit Patel (11) were at the crease when stumps were draw for the day at Sardar Patel Stadium B Ground. Bell has already smashed nine boundaries, including three sixes in his innings.
Except for skipper Amit Mishra, none of Haryana's bowlers has played international cricket and both Pietersen and Cook relished the batting practice ahead of the Test grind.
Mishra took two of the three England wickets to fall.
Pietersen, who hit 16 fours and three sixes, is the fourth England batsman to hit a century after arriving in India with Cook and Samit Patel reaching the three-figure mark against India A.
Reserve wicket-keeper Jonny Bairstow had stroked his way to a hundred against Mumbai A in the last game.
Cook, who was dropped early in his innings, scored a boundary-filled 97 with 18 hits to the fence. Nick Compton (74) also staked a claim for the opening slot in the first
Test with his second successive half-century.
The two openers put on 166 before Cook was caught by wicket-keeper Sandeep Singh off spinner Jayant Yadav.
Jonathan Trott replaced the skipper at the wicket and he too got some runs under his belt ahead of the first Test. In the company of Compton, Trott added 45 runs before the former was trapped in front of the wicket by leggie Mishra.
Compton, who played 111 dot balls during his stay at the crease, hit nine boundaries and a six in his 144 ball-innings.
The fall of Compton brought Pietersen to the wicket. He began with a boundary, a flick to the mid-wicket off Amit Vashisht before hitting two more crisp boundaries of spinners.
At tea, Trott was unbeaten on 45 off 76 balls with seven boundaries and Pietersen had settled well, reaching 18 off 22 balls with three boundaries.
Trott fell leg before wicket to Mishra, his second scalp, immediately after the tea-break for 46, which brought Ian Bell to the middle. Bell also started aggressively and hit a six of Mishra before hitting another four and a six of the leggie.
Bell and Pietersen attacked the Haryana bowlers relentlessly and England reached their 300 in the 69th over. Pietersen retired out to allow Samit Patel spend some time on the wicket and get acclimatised to the playing conditions.
When play ended, Patel had hit two boundaries in his 11-run unbeaten knock while Bell had batted his way to a half-century.