The hosts, who will recapture the urn with victory in Perth, having won the first two Tests in the series, looked in real trouble with the dismissal of George Bailey before tea reduced them to 143 for five.
Smith and wicketkeeper Brad Haddin, however, combined to put on 124 for the sixth wicket with circumspect, and on occasion aggressive, innings that contrasted sharply with the cavalier earlier efforts of some of their team mates.
- Photos: Third Ashes Test, Day 1
They were separated when Haddin, who has scored half centuries in all four of his innings in the series, spooned the ball to James Anderson at midwicket off the bowling of Ben Stokes for 55 an hour before the close of play.
When stumps were drawn for the day, Australia were 326 for 6 after 87 overs.
Smith continued to reach his second Test century and will resume on Saturday on 103 not out with Mitchell Johnson, unbeaten on 39, alongside him.
After losing the toss for a third straight match and the chance to bat on what looked like an excellent surface, England responded to their do-or-die situation with their sharpest display in the series to date.
Australia's batsmen looked intent on piling on the runs as quickly as possible - they were scoring at five an over at one stage - but also contributed to their own demise with some rash strokes.
David Warner's attempted cut only to be caught at point for 60 would contend for the softest dismissal of the day but Bailey (seven) also came close to claiming the honours with an attempted hook that saw him hole out on the boundary.
Captain Michael Clarke (24) will also be disappointed with the shot that led to his departure just before lunch, a wicket which followed the run out of opener Chris Rogers (11) and dismissal of Shane Watson (18) in the first hour.
DANCED A JIG
England spinner Graeme Swann, under pressure after disappointing displays in the Brisbane and Adelaide defeats, made a significant contribution by catching Watson well in the slips before accounting for dangermen Clarke and Warner with his bowling.
Seamer Stuart Broad took the wickets of Watson and Bailey and England, if not in charge, certainly had the upper hand at a ground where they have not won since 1978.
Smith had already signalled his intent with a big six to get off the mark, however, and when he was joined in the middle by Haddin, Australia's rearguard was in place.
While Smith played his scoring shots almost exclusively to the on side, Haddin favoured off but they both brought up their half centuries from 76 balls with five fours and two sixes.
With the temperatures out in the middle now exceeding 40 degrees Celsius, the pair forced England to labour long into the extended afternoon session under the blazing Perth sunshine.
Haddin had performed his country a similar service on the first day of the series opener in Brisbane, coming in with Australia at 132 for six and rescuing the innings with a gritty 94.
After he had finally departed to shatter the late afternoon torpor that had descended on the ground, Smith reached his century with a sublime pulled four off a short ball from Stokes and danced a jig in celebration.
England's hopes of another breakthrough were thwarted by a 59-run partnership between Smith and the obdurate Johnson, the bowling hero of the first two Tests.
Image: Steve Smith of Australia celebrates after scoring a century during Day 1 of the Third Ashes Test against England at WACA.
Photograph: Quinn Rooney/Getty Images
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