Australia captain-elect Steve Smith ended England skipper Alastair Cook's marathon resistance as the tourists eyed a consolation win in the fifth and final Ashes Test at The Oval on Saturday.
At stumps on the third day, England, following-on, were 203 for six - still 129 runs behind Australia's first innings 481, which featured Smith's 143.
It looked as if left-handed opener Cook would bat until the close.
But outgoing Australia captain Michael Clarke's typically inventive decision to bring on Smith in the 77th over yielded a quick dividend when the part-time leg-spinner struck with just his sixth ball as Cook was caught of bat and pad by Adam Voges at short leg.
Cook, who has never scored an Ashes hundred in England, was out for 85 having batted for more than five-and-a-half hours while facing 234 balls including 11 fours.
At the close, wicketkeeper Jos Buttler was 33 not out, with nightwatchman Mark Wood - who kept out a thunderbolt Mitchell Starc yorker off the last ball of the day - unbeaten on nought.
England, however, at least had the consolation of having won the Ashes at 3-1 up in the five-match series.
They resumed Saturday on 107 for eight in their first innings, a deficit of 374 runs.
Moeen Ali, whose 30 was the top score of the first innings and Wood (24), both eight not out overnight, hit out in sunny conditions ideal for batting during a ninth-wicket partnership of 57.
They fell to successive Mitchell Johnson deliveries, with England bowled out for 149.
Clarke then became the first Australia captain to enforce the follow-on in a Test since Ricky Ponting did so against New Zealand at Wellington in 2010 - a match Australia eventually won by 10 wickets.
Opener Adam Lyth, desperate for a big score to cement his England place, fell for 10 when he edged a good length ball from Peter Siddle that cut away off the pitch to Clarke at second slip.
Lyth's dismissal meant he had scored just 115 runs in nine innings this series at an average of 12.77
Siddle, whose recall for this match was deemed a "panic" measure by Australia great Shane Warne had stumps figures of one for 14 in 16 overs - including 10 maidens.
Ian Bell, on nine, saw a pull off Mitchell Marsh sting the fingers of Chris Rogers at mid-wicket before going for four.
But next ball lively seamer Marsh got a delivery to leap off a length and it took Bell's glove before lobbing gently to Clarke, who will retire from international duty after this match.
Joe Root, England's leading run-scorer this series, then became the latest home batsman this match to give his wicket away playing a careless cross-bat shot when a top-edged pull off Johnson flew straight to Starc at fine leg.
Root's exit for 11 left England 99 for three.
England had lost their last seven first-innings wickets for just 46 runs during Friday's evening session.
Another equally steep collapse loomed when off-spinner Nathan Lyon took two wickets for no runs in five balls to leave England 140 for five.
Jonny Bairstow (26), fell when an inside edge was caught at the second attempt by Voges at short leg.
Replays suggested Bairstow had been unlucky as the ball had hit Voges's protective helmet and so should have been ruled a dead ball.
Curiously, the Yorkshireman was out in similar fashion in Mumbai in 2012/13.
Ben Stokes exited for a duck, when he needlessly pushed out at a Lyon ball that turned away from the left-hander and edged a simple catch to Clarke at slip.
Players from both sides wore black armbands in memory of Australia's Arthur Morris, one of Test cricket's greatest opening batsman, whose death at the age of 93 was announced on Saturday.