Cheteshwar Pujara resumed in the morning on 98 and reached 206 not out as India built their advantage steadily, before declaring with 18 overs left in the day.
England looked to survive until the close, but India's spinners picked up three wickets in three overs to leave the tourists in a mess with three days still to play.
Debutant Nick Compton took most of the strike, and his technique held up well for 52 balls until Ravichandran Ashwin bowled him through the gate for nine runs.
James Anderson was sent in as a nightwatchman with 20 minutes of the day remaining, but was quickly exposed, perishing for just two after a sharp bat-pad catch by Gautam Gambhir off the bowling of Pragyan Ojha.
That brought the man he was protecting, Jonathan Trott, to the crease, and he departed in the same fashion for a four-ball duck to Ashwin, Pujara capping off an excellent day with the catch.
Kevin Pietersen (six) and Alastair Cook (22) took England through to stumps, a very distant 480 runs adrift of their hosts.
With scoreboard pressure on their side and spinners into the fray from the very first over, India's bowling was in stark contrast to England's, with the tourists having been wicketless through the first session once again.
Pujara quickly reached his second Test century, while Yuvraj Singh for the most part reined in his attacking instincts to play sensibly as an effective foil. The extravagant strokeplay of day one was absent, but the accumulation was patient and, barring a couple of leg-before shouts from Graeme Swann, chanceless.
Yuvraj, playing his first Test since a battle with cancer, looked set for a sensational comeback ton, but one rash stroke on 74, holing out in the deep after a waist-high full toss from Samit Patel, ended his knock after lunch.
Captain MS Dhoni became Swann's fifth victim, gloving the ball on to the stumps after a botched sweep for five, while Ashwin (23) and Zaheer Khan (seven) kept Pujara company as he casually moved to his double-century.
It looked as if India were quite happy to bat all day, and while the declaration came as something of a surprise, it proved to be an inspired move.