Mitchell Starc of Australia takes the wicket of James Vince of England. Photo / Getty
Australia are well placed to reclaim the Ashes with an emphatic victory in the third Test, having broken records with the bat then reduced England to 132-4 on day four at the WACA.
Australia posted their highest total in a home Ashes Test innings, declaring at 662-9 some three and a half overs after Sunday's meal break.
England require a further 127 runs to make the hosts bat again.
The enormity of their challenge was underlined by a near-unplayable delivery from Mitchell Starc that straightened after hitting a crack then uprooted James Vince's off stump.
Heavy rain stopped play some five minutes before the scheduled tea break on day four. The day's final session started on time but swirling showers soon had the Barmy Army dancing in their seats, with the umpires finally calling for the covers at 4.45pm local time. The players would not return.
More rain is predicted on the final day of play.
Visiting captain Joe Root may need a downpour of biblical proportions to keep the series alive after his summer of woe continued on Sunday.
Root was undone by Nathan Lyon's first delivery of the innings. Fittingly it was Smith who clutched the edge that careered off Tim Paine's gloves, sealing the fate of the tourists' most talented batsman.
The captains' battle within a battle has been a no-contest. Smith is set to collect his second man-of-the-match award of the series and has 426 runs at 142; Root has managed 176 runs at 29.
Vince was obstinate during a 95-ball stay at the crease but on 55 was left gobsmacked by a sensational ball from Starc.
Josh Hazlewood, bowling with the confidence created by a first-innings lead of 259 runs, dismissed both openers in a fired-up opening spell.
Hazlewood held a sharp return catch to remove Alastair Cook for 14, while Mark Stoneman was caught behind after prodding forward to a ball on a good length.
Earlier, Smith and Mitch Marsh were unable to extend their game-changing partnership of 301 runs.
Tim Paine and Pat Cummins further demoralised England in a 93-run stand, during which Root set defensive fields and opted against taking the third new ball as he waited for Smith to declare.