Each of India's top five batters, including debutant Devdutt Padikkal, managed 50-plus scores to power the hosts to a commanding 473-8 for a lead of 255.
Ben Stokes claimed a wicket with his first ball in eight months, and James Anderson inched closer to his 700th test wicket, but India, holding an unassailable 3-1 lead in the series, looked in control of the contest.
Kuldeep Yadav (27) and Jasprit Bumrah (19) have raised 45 useful runs for the unbroken ninth wicket and they will resume on Saturday hoping to take India past the 500 mark.
India have been in the ascendancy since bowling out England for 218 on the first day at the picturesque Himachal Pradesh Cricket Association Stadium.
Overnight batters Rohit and Gill went after the bowlers right from the word go.
The one shot that epitomised their approach was when Gill stepped out against Anderson and hit test cricket's most successful fast bowler over his head for a six.
"I thought the ball wasn't doing much at that time," said Gill, who smashed 110.
"I wanted to go over the top to put some pressure on him, and that's why I played that shot."
Spinner Shoaib Bashir got a flick from Rohit but the ball flew past Zak Crawley before the fielder could even cup his hand.
Rohit took a single off Tom Hartley to bring up his hundred, while Gill slog-swept Bashir for a four in the next over to complete his century.
Stokes, who underwent knee surgery in November, resumed bowling duties with a magical delivery that hit the top of Rohit's off-stump. Rohit's mature 103 included three sixes.
Anderson flattened Gill's off-stump in the next over to claim his 699th test wicket. Gill smacked five sixes in his stellar knock.
"I think I missed out on a big one," the number three batter said.
"Even the ball that I got out to, I could not sight it properly.
"Apart from that, I'm feeling good, and hopefully I'll be able to convert these starts into big ones."
The collapse England wanted did not materialise as Sarfaraz Khan (56) counter-attacked.
The 26-year-old played an audacious ramp shot against Mark Wood and pulled the fast bowler for a six en route to his third fifty of his debut series.
Padikkal (65) hit Bashir for a six to bring up his fifty before the off-spinner produced a three-wicket burst.
Sarfaraz perished in the slip, Padikkal lost his off-stump and Dhruv Jurel holed out in the deep. Bashir finished with figures of 4-170.
Tom Hartley joined the party removing Ravindra Jadeja and Ravichandran Ashwin in the same over.
