Teenage opener Sam Konstas continued his difficult introduction to Test cricket, falling for a four-ball duck - his third single-figure score in four innings - bowled by a fired-up Jayden Seales.
The West Indies pacer then trapped Usman Khawaja lbw for just 2, leaving the veteran opener without a score above 20 in three innings this series.
Seales' double-strike came inside the first three overs of Australia's second innings, capping an impressive day for the right-armer, who now has nine wickets in the series.
Earlier, Australia had bowled West Indies out for 253, securing a 33-run lead after their own first innings of 286.
Brandon King stood out for the hosts with a maiden Test half-century, scoring 75 and sharing key stands with John Campbell (40), Roston Chase, and Shai Hope. He was eventually dismissed between Chase and Kavem Hodge.
A spirited eighth-wicket partnership of 51 between Alzarri Joseph and Shamar Joseph added late resistance before Nathan Lyon claimed both King and Joseph in a tidy spell that yielded 3 for 75.
Pat Cummins and Josh Hazlewood contributed with two wickets apiece, including Hazlewood's dismissal of Kraigg Brathwaite for 4 - mirroring the West Indies skipper's scores from both innings in the first Test.
With the series finely poised, Australia will aim to recover from their shaky start on day three, while the West Indies look to build on Seales' momentum in pursuit of a series-levelling victory.
Australia's top-order frailties came under scrutiny once more as they were bowled out for 286 on the opening day of the second Test against West Indies at the National Stadium in St George's.
Shubman Gill's colossal 269 runs powered India to a commanding 587, setting the stage for a ruthless bowling display that left England reeling at 77-3 after day two of the second Test at Edgbaston.
India choosing to rest their premier strike bowler Jasprit Bumrah in the midst of a vital Test series has left many cricket fans scratching their heads.
Shubman Gill continued his dream start to captaincy with a second consecutive Test century, steering India to 310 for 5 on the opening day of the second Test against England at Edgbaston.
