The 24-year-old Cheteshwar Pujara scored an unbeaten 206 and batted for close to nine hours before the hosts declared the first innings at 521 for eight shortly after the tea break on the second day and then reduced the visitors to a precarious 41 for three at stumps.
Captain Alastair Cook (22) and Kevin Pietersen (6) were the two unbeaten batsmen at close with England still needing 281 runs to avoid the follow on.
Nick Compton (9), James Anderson (2) and Jonathan Trott (0) are the three batsmen back in the pavilion on a Sardar Patel track which has already started taking turn.
It was Pujara who hogged the limelight as he not only recorded his second Test century in his sixth match but showed his class with some glorious shots on both sides of the wicket.
The left-handed Yuvraj Singh, playing his first Test since recovering from a rare germ cell cancer, was the other notable performer with a fluent 74 while captain Mahendra Singh Dhoni (5) and R Ashwin (23) and Zaheer Khan (7) could not hang around for long.
Off-spinner Graeme Swann was the pick of the English bowlers with figures of 51-8-144-5, recording his 14th five wicket haul in an innings.
Pujara became only the sixth Indian batsman to hit a double century against England. He joined the list of Mansoor Ali Khan Pataudi, Sunil Gavaskar, Gundappa Viswanath, Vinod Kambli and Rahul Dravid.
Pujara batted for a marathon 513 minutes, faced 389 balls and struck 21 fours during his epic unbeaten knock which served as the foundation for India's monumental total.
Off-spinner R Ashwin, who opened the bowling, scalped two wickets and in the process became the fastest Indian to claim 50 Test wickets in his ninth Test, eclipsing Anil Kumble's record of achieving the feat in his tenth match.
India 1st innings: (overnight 323-4)
Gautam Gambhir b Swann 45
Virender Sehwag b Swann 117
Cheteshwar Pujara not out 206
Sachin Tendulkar c Patel b Swann 13
Virat Kohli b Swann 19
Yuvraj Singh c Swann b Patel 74
M S Dhoni b Swann 5
R Ashwin c Prior b Pietersen 23
Zaheer Khan c Trott b Anderson 7
Pragyan Ojha not out 0
Extras (B 1, LB 10, NB 1) 12
Total (for 8 wkts decl, 160 overs) 521
Fall of wickets: 1-134, 2-224, 3-250, 4-283, 5-413, 6-444, 7-510, 8-519
Bowling: James Anderson 27-7-75-1, Stuart Broad 24-1-97-0, Tim Bresnan 19-2-73-0, Graeme Swann 51-8-144-5, Samit Patel 31-3-96-1, Kevin Pietersen 8-1-25-1.
England 1st innings:
Alastair Cook not out 22
Nick Compton b Ashwin 9
James Anderson c Gambhir b Ojha 2
Jonathan Trott c Pujara b Ashwin 0
Kevin Pietersen not out 6
Extras (LB 2) 2
Total (for 3 wickets in 18 overs) 41 Fall of wickets: 1-26, 2-29, 3-30 Bowling: Ravichandran Ashwin 8-1-21-2, Zaheer Khan 5-3-6-0, Pragyan Ojha 4-1-3-1, Yuvraj Singh 1-0-9-0.