Adam Voges became the 20th Australian to score a test century on debut overnight as he helped Australia to a first innings lead of 170 runs.
The West Indies dismissed Australia for 318 shortly after tea, as the hosts then reached 2-25 at stumps on day two.
Voges was the only shining light for Australia, as his teammates crumbled around him.
The Test debutant scored 130 not out from 247 balls, including 13 fours and one six.
No. 11 batsman Josh Hazlewood was the next highest scorer with 39.
Australia resumed at 3-85, with Smith the other not out batsman with Voges.
However, Smith fell soon after the resumption of play when he was stumped for 25 off the bowling of Bishoo.
Watson then became Bishoo’s third victim of the innings, as he was dismissed for 11 soon after.
Wicket-keeper Brad Haddin then received one of the best balls he has likely faced in his career. Bishoo ripped a superb leg break to take out Haddin’s off stump and send the Aussie packing. Amazingly, the home side was now in the match, with the Aussies struggling at 6-126.
Mitchell Johnson (20) then combined with Voges for a 52 run stand to see Australia past the Windies total of 148, before Bishoo removed Johnson for his fourth scalp of the innings.
Bishoo then claimed the wicket of Starc just two balls later for a duck, before Gabriel removed Lyon for 22 to leave the Aussies at 9-221.
It appeared that Australia would only have small lead to defend heading into the second innings, thanks to some great bowling and a difficult pitch to bat on.
But Josh Hazlewood and Adam Voges had other ideas.
The pair shared a 97-run 10th wicket partnership to steer Australia to a dominant position and frustrate the Windies bowling attack.
Bishoo was the pick of the bowlers, taking career best figures of 6-80.
West Indies openers Brathwaite and Hope combined for a 21 run opening stand at the resumption of play, before Johnson and Starc struck in successive balls to leave the hosts in a difficult position at 2-25 at stumps.
Shane Dowrich is not out with one run to his name, while Darren Bravo has three.