Four years after his iconic first-ball dismissal of Rory Burns at the Gabba, Australia's left-arm spearhead finished the opening over of this series with the wicket of Zak Crawley (0).
Starc (3-24) wasn't done there, claiming Crawley's opening partner Ben Duckett (21), and most importantly, star batter Joe Root (0).
After Ben Stokes, surprisingly, chose to bat first after winning the toss, England limped to lunch at 4-105.
No.3 Ollie Pope and the aggressive Harry Brook (28*) went about trying to salvage England's innings, coming together at 3-39.
But after being hit for 10 runs, Cameron Green trapped Pope (46) lbw with the final ball of his first over.
Making matters worse for England is Pope and Duckett burned two of their three reviews.
Stokes (4*) joined Brook in the middle, the pair making it to the break.
A Perth record crowd of 43,591 was already in the stadium to see Starc claim a wicket in the first over of a Test for the 24th time.
Starc getting Root caught in slips took him to 100 Ashes dismissals, and 405 in his career.
"This guy is a bowler of the ages and we've taken him for granted for so long," former Australia spinner Kerry O'Keeffe said on Fox Cricket.
Without captain Pat Cummins and fellow injured quick Josh Hazlewood, Starc became the clear leader of Australia's pace attack.
As promised, England went about attacking Scott Boland (0-39 from seven overs), who opened the bowling with Starc.
Former England captain Mike Atherton talked down Boland's prospects pre-series, believing Australia didn't have the same fear factor without Cummins.
Quick Brendan Doggett and aggressive opener Jake Weatherald are on international debut, making it the first time Australia have blooded two debutants in the same Test since January 2019.
Doggett became Australia's 472nd Test cricketer and was presented with his baggy green by fellow late bloomer Boland and former star quick Jason Gillespie.
Boland and Doggett are creating history as the only two Indigenous players to be in the same Australian Test team.
Doggett is just the third First Nations man to play Tests for Australia, after Boland and Gillespie.
The 31-year-old had an encouraging first session of his Test career, going to lunch with figures of 0-17 from his five overs.
Weatherald, who grew up in Darwin before emerging as a domestic cricketer in South Australia, was handed his first cap by former Australia champion David Warner.
He is Usman Khawaja's sixth opening partner since Warner retired from Test cricket in January 2024.
After picking a 12-man squad on Wednesday, England on Friday confirmed they had left out spinner Shoaib Bashir in preference for express quicks Mark Wood and Jofra Archer.
Two of the quicker bowlers in the world, Wood and Archer have never played together against Australia in the same Test.
They will partner Gus Atkinson and Brydon Carse, with Stokes also to bowl pace.
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