Peter Siddle, returning after almost nine months in the Test wilderness, grabbed two wickets while Joe Root was out for six on review.
Mitch Marsh ran through the middle order, snaring 3-4 in 14 balls including the prized scalp of Root.
The allrounder should have had a fourth wicket and England should have been 9-96, with Mark Wood edging straight to first slip Adam Voges.
However, Mark Wood was recalled after replays revealed it was a no-ball.
Michael Clarke and Chris Rogers are nonetheless perfectly placed to retire on a high note, provided rain does not ruin the dead rubber.
However, there will be a sense of what-if for the tourists if they end up losing the five-Test series 3-2 as expected.
Clarke's men ceded the urn by losing the fourth Test in Nottingham, where they were rolled for 60 after being asked to bat first on a green deck.
If they had of exercised the same patience with bat and ball that was on display in London, it may well have been Australia's first UK Ashes win since 2001.
"That's the best we've bowled all series," Smith said, deflecting praise.
"They created a lot of pressure.
"We didn't give them runs, we made them earn their runs."
Smith put the game on Australia's terms, playing conservatively for the majority of his 394 minutes at the crease.
He shared a partnership of 146 runs with Adam Voges then a 91-run stand with Mitchell Starc.
Smith became the leading run-scorer of the series plus the first Australian since Matthew Elliott in 1997 to score 500 runs in an away Ashes.
The 26-year-old remained obstinate as the hosts bowled well wide of his off stump to dry up the runs,
The glaring exception was in the 94th over, when the 26-year-old was on 92 and fished at a wide ball from Steve Finn.
Wicketkeeper Jos Buttler gleefully accepted the edge, but replays showed Finn clearly overstepped.
Marsh was guilty of the same sin, but the punishment is unlikely to be as severe.
Nathan Lyon started the rot when he ended the second session with a magnificent delivery that turned sharply and kissed the top of Alastair Cook's off stump.
Siddle created the next two breakthroughs, Adam Lyth mistiming a pull shot and Ian Bell clean bowled by a beautiful delivery.
- AP