Australia have bundled out India for 244 in the day-night Test at Adelaide Oval, after the visitors resumed the day at 233/6 overnight.
Tim Paine and CO. took just 22 minutes and 4.1 overs on Friday to take remaining four wickets, to gain advantage over their rivals.
India looked good at one stage in the game with Kohli and Rahane in the middle but with the former getting run out after shambolic mix-up between the wickets menat the side lost its flow.
On Friday morning, Pat Cummins got Ravichandran Ashwin caught behind with the third ball of the day.
Starc then struck with his third delivery of the day, removing Wriddhiman Saha after the Indian skipper was caught chasing the ball outside the off stump.
Starc also fired out Umesh Yadav to finish with figures of 4-53 from 21 overs as he enhanced his reputation as the world's premier pink-ball bowler.
"We all know how good a bowler he is, then you throw a pink ball into his hands and he grows an extra pair of legs," Nathan Lyon said of Starc.
"He's exceptional and the way he came back and started, after having some personal leave, was absolutely incredible.
"I wouldn't expect anything less from Mitch, he's a world-class player."