Australia were 397 for six at tea on a rain-affected second day of the fifth Test, with Smith 112 not out and debutant James Faulkner one not out as they sought a consolation win after England had already taken the series at 3-0 up.
The tourists resumed well-placed on their overnight 307 for four after rain delayed Thursday’s start by three-and-a-half hours.
Smith was 66 not out and nightwatchman Peter Siddle 18 not out following Shane Watson’s Test-best 176 on Wednesday.
The glare of The Oval floodlights did little to mask the gloom, with the overcast conditions more bowler-friendly than Wednesday’s sunny blue skies when England debutants Chris Woakes, a seam-bowling all-rounder, and left-arm spinner Simon Kerrigan took none for 105 in 23 overs between them.
It did not take long for paceman James Anderson, who on Wednesday moved past Bob Willis into second place in England’s all-time list of leading Test wicket-takers, to make the breakthrough.
Anderson bowled Siddle for 23 with a superb delivery that swung in to the right-hander before moving away off the pitch to clip the top of off stump.
New batsman Brad Haddin was on 15 when England had an appeal by wicketkeeper Matt Prior for caught behind off Anderson turned down.
It looked as if the ball had missed the batsman’s bat and gloves and umpire Kumar Dharmasena’s verdict was upheld by the Decision Review System.
Woakes, albeit in more helpful circumstances, bowled better than he had on Wednesday but when he dropped short Smith was quickly into position to pull him for a four that took the batsman to 89 — the same score he made in the drawn third Test at Old Trafford.
But, as Graeme Swann and fellow spinner Kerrigan waited to bowl Thursday, the 24-year-old Smith, playing the 12th Test of a career that saw him initially regarded as a leg-spinner who batted, went to his hundred in style by on-driving occasional medium-pacer Jonathan Trott for six.
Smith faced 198 balls, including 14 fours and two sixes, for his century.
However, four balls later, Haddin, trying to cut, became Trott’s fifth Test wicket when he played on for 30.