Steve Smith scored his 31st Test century before Australia captain Pat Cummins sparked India's collapse in the World Test Championship final on Thursday.
Smith, 95 not out overnight, followed team-mate Travis Head in going to three figures with 121 in a first-innings total of 469 at The Oval.
Fast bowler Cummins, in his 50th Test, then removed opposing skipper Rohit Sharma to initiate India's second-day slump.
Ajinkya Rahane (29 not out), struck some painful blows on the glove, held firm with Ravindra Jadeja (48) after India had been reduced to 71-4.
But India were 151-5 at stumps, a huge deficit of 318 runs.
Rohit was plumb lbw for 15 to a full-length ball from Cummins, who had close figures of 1-36 in nine overs.
Four balls later, India were 30-2 when Shubman Gill (13) was bowled playing no shot to Scott Boland after being deceived by a sharp off-cutter.
England's Stuart Broad tried to rile Australia before this match by saying he hoped Cheteshwar Pujara and Virat Kohli kept Cummins's men in the field for a long time ahead of next week's first Ashes Test at Edgbaston.
But both senior India batsmen fell for 14 on Thursday.
Pujara was bowled leaving a delivery from all-rounder Cameron Green and Kohli was undone by a spiteful, lifting ball from Mitchell Starc that took the shoulder of the bat, with Smith holding an excellent leaping catch above his head at second slip.
Left-hander Jadeja defied Australia in an aggressive 51-ball knock featuring seven fours and a six.
But he succumbed to off-spinner Nathan Lyon, edging a well-flighted and turning delivery to slip in a tame end to a stand of 71 with Rahane.
- 'Really good spot' -
"We are in a really good spot so hopefully we can get a few more wickets in the morning," Boland told Sky Sports.
"The pitch is going a little bit up and down so it should be harder for the India batters tomorrow (Friday)."
India were facing a potentially huge Australian first-innings total with Smith and Head (163) at the crease.
But their pacemen struck as Australia lost four wickets for 41 runs, including Head and Smith, to slip from 361-3 to 402-7.
India bowled out Australia after lunch, fast bowler Mohammed Siraj taking 4-108 from 28.3 overs.
Smith reached three figures in the opening over on Thursday, joining compatriot Steve Waugh on seven Test hundreds in England.
Among non-England batsman, only Australia great Don Bradman, with 11 centuries, has scored more.
Smith's 31st Test century left him 12th on the all-time list.
Head extended his first overseas Test century to 150 but a short ball proved his undoing when he tried to whip Siraj legside and gloved a catch to wicketkeeper Srikar Bharat.
Head's dismissal ended an impressive stand of 285 runs with Smith after they had come together with Australia in trouble at 76-3.
Shardul Thakur then captured the prized wicket of Smith, who inside-edged an outswinger into his stumps to the delight of the large India contingent in a crowd of over 23,000.
The WTC is the only major men's cricket trophy Australia have yet to win.
India are appearing in their second WTC final, having lost to New Zealand in the inaugural 2021 showpiece match in Southampton.
jdg/smg/iwd
