Simon Harmer led South Africa's charge on day one of the third Test in Nagpur with four wickets as India were bowled out for 215.
Virat Kohli's decision to bat having won the toss dramatically backfired as his side were skittled out, with Morne Morkel (3-35) also at the forefront.
A 50-run opening partnership hinted at a positive day for the hosts - who lead the four-match series 1-0 - but once Shikhar Dhawan (12) fell in the 14th over their day began to unravel.
Wickets fell at regular intervals throughout Wednesday with Morkel softening up the top order, before Harmer (4-78) ripped through the tail on a turning pitch.
Only Wriddhiman Saha (32) and Ravindra Jadeja (34) provided any resistance until Harmer closed things out with the dismissal of Amit Mishra (3) with 11 overs remaining in the day.
In their reply the Proteas found the conditions equally as challenging, Stiaan van Zyl (0) and nightwatchman Imran Tahir (4) falling to spin as they closed 204 runs behind.
Dhawan and Murali Vijay (40) offered India early promise as they made a watchful start, the latter playing a more aggressive role as he attacked on the leg side.
In a sign of things to come spin made the first breakthrough as an advancing Dhawan got an inside edge to give Dean Elgar (1-7) a simple catch off his own bowling.
That opening gave plenty of hope to Harmer as he picked up the wicket of Cheteshwar Pujara (21), but Morkel's contribution was almost as telling.
A disciplined spell of fast bowling saw Vijay, Ajinkya Rahane (13) and Kohli (22) all fall to the 31-year-old, the India captain getting a beautiful seaming delivery that forced an edge behind.
His job done, Morkel watched on as South Africa's spinners made India toil, Harmer using the pitch to his advantage to claim his third four-wicket haul in five Tests.
Faced with a tricky nine-over spell at the end of the day, South Africa took 15 deliveries to get off the mark as India's spinners quickly found their rhythm.
Ashwin got the better of Van Zyl for the fourth time in the series to give India their first wicket and Tahir - who had already survived a stumping attempt - followed him back after one lusty blow to the boundary.