With West Indies chasing 204 for victory in the third Test in Jamaica, Starc took three wickets in the first over alone as the hosts fell to 6-22 at tea on day three.
Playing in his 100th Test, Starc also became the fourth Australian to reach the 400-wicket milestone and joined greats Shane Warne, Glenn McGrath and Nathan Lyon.
And the left-armer did it in style, ripping the heart out of West Indies with a record-breaking spell at Sabina Park of 5-6 from five overs at Sabina Park.
Starc's 15-ball five-wicket haul marked the fastest by any bowler in Test history, beating Ernie Toshack from 1947, Stuart Broad's 2015 Trent Bridge effort and Scott Boland's MCG heroics of 2021.
Each of those took 19 balls.
Starc also became the second man to take three wickets in the opening over of an innings, striking when he had John Campbell caught behind first ball.
He then trapped Kevlon Anderson lbw when the right hander left a ball that tailed in at him, before bowling Brandon King with the last ball of the over.
Starc's assault carried into his third over, claiming his 400th Test wicket with another ball that swung into Mikyle Louis' back pad.
Shai Hope followed two balls later, again trapped lbw.
At that point Starc had figures of 5-2, with the only runs off him coming off the outside edge of Hope's bat and through the slips.
Starc could have had another wicket before tea, had Sam Konstas not grassed a chance at third slip to remove Alzarri Joseph on 0.
Josh Hazlewood also picked up one wicket in the collapse, getting Roston Chase caught behind and denying Starc the shot at all 10 wickets.
In all, four of the West Indies top five were dismissed for ducks, with Louis the only one to trouble the scorers with a four when he edged Hazlewood to the boundary.
Starc's record showing came after Australia had appeared in danger of dropping the Test, when bowled out for 121 in their second innings.
After resuming on Monday (Tuesday AEST) at 6-99, Australia lasted just eight more overs with Cameron Green bowled from the first ball of play.
Australia's best batter on day two, Green lost the top of his off stump when he left a Shamar Joseph ball that seamed back in at him.
Shamar and Alzarri Joseph then cleaned up the tail, with the latter finishing with 5-27 after doing the damage under lights on Sunday.
Australia's total marked their lowest against West Indies since Courtney Walsh and Curtly Ambrose were wreaking havoc in 1995.
But any prospect of that costing the visitors a shot at a 3-0 series clean sweep were abruptly ended by Starc's new-ball heroics.
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