Joe Root’s men did their utmost to frustrate Smith by drying up his run-scoring options, but he refused to be distracted for more than eight and a half hours in his unbeaten 141 as Australia scrambled to 328 all out and a lead of 26.
England then made a miserable start to their second innings against Josh Hazlewood on the way to 33-2, with the early loss of Alastair Cook for his second single-figure score in three days and then James Vince - unable to follow up his maiden Ashes half-century here.
That was 17-2, and only a run later still scoreless Root had his helmet rearranged by a brute of a bouncer into the side of the grille from Mitchell Starc.
A torrid time continued for the England captain and opener Mark Stoneman, as Pat Cummins also bowled a rapid and menacing spell up to stumps - but they stood firm.
Smith’s was a tour-de-force performance, entirely fitting of a home captain out to put his stamp on this Ashes series from the outset.
His opposite number, and England’s attack bowling to order, made him scrap for every run as they put a block on his options with a stalemate leg-side field and no leeway to hit through the off.
Smith was therefore restricted to just 17 runs before lunch and did not register his 50th of the day until the first ball after tea.
He refused to panic, though, and received very significant support.
It came first from Shaun Marsh (51), Australia’s returning No 6 who did the bulk of his work the previous evening but was a more than equal partner in a fifth-wicket partnership of 99 and completed his deserved half-century before a curious mis-drive at Stuart Broad (3-49) to hole out at mid-off.
The second new ball then accounted for Tim Paine and Starc inside two overs.
Paine was very well-caught behind by Jonny Bairstow off James Anderson, and Starc followed a memorable six off Broad over long-off to get off the mark third ball by falling to his fifth when he poked a return chance back to the same bowler.
It was Cummins who did most to help Smith ensure the first innings lead, batting well above the pay grade of a number nine with organised defence and attacking flair to match until Chris Woakes broke his duck for the series when he had him edging to a tumbling Cook at second slip.
Smith still managed to engineer another 53 for the last two wickets and, after barely a false shot to any of his 326 balls, he was still in situ when Nathan Lyon was neatly caught at leg-slip by Cook off Root.
England had rarely looked like getting him out at any point on this untypically slow Brisbane surface.
Yet as soon as it was the tourists’ turn to face the new ball again, everything seemed to be happening too quickly for them.
Cook’s mode of dismissal, to a mishook to long-leg, was especially concerning - and then Vince came and went quickly, caught at second slip in the fashion many had predicted he might during this series.