Just before Lunch, the visitors added 100 runs in first session but lost three more wickets with skipper Faf du Plessis leading the fight against India's phenomenal bowling attack by attaining a courageous fifty.
Just after two overs post Lunch, Jadeja got his first wicket by handing spinner Senuran Muthusamy (7) his first dismissal in Tests.The Indian all-rounder trapped Muthusamy in front of stumps (LBW out) with a sharp turning delivery.
Captain du Plessis alongside Vernon Philander tried batting cautiously against the spin duo of Ashwin and Jadeja, attacking from both ends. Faf's (64 off 117) resistance came to an end after Ashwin bowled a 'spinner's delight' to get his outside edge with deputy skipper Rahane completing an easy catch at first slip.
Earlier, India speedsters Umesh Yadav and Mohammed Shami dominated the Proteas batsmen to leave them reeling at 136/6, trailing by 465 runs at Lunch on Day 3 of the second Test at Pune.
It was for the first time since 2001 that top five batsmen were dismissed by India's pace bowlers in a home Test innings.
South Africa's 75-run stand between Quinton de Kock- Faf du Plessis was broken by R Ashwin, just before lunch.
Team India had plenty in their kitty to stay happy as South Africa were struggling on 36/3 and trailed by 565 runs with 7 wickets remaining in their innings at stumps on Day 2.