India off-spinner Ravichandran Ashwin took the wicket off the first delivery of the second innings when he dismissed England's Rory Burns. The English opener failed to adjust to the delivery which drifted away from the left-hander, inducing an outside edge.
Ajinkya Rahane was sharp at the slips as he took a leap towards his left to take the catch.
With this wicket, Ashwin became the first spinner in over 100 years to take a wicket off the first ball of an innings. The last spinner to achieve this feat was South Africa's Bert Vogler in 1907.
Justifiably, he is also the first Indian to achieve the feat.
Earlier, Responding to England's mammoth 578, India were all out in 95.5 overs and fell well short of the follow-on target despite Washington Sundar's fighting knock of 85.
Rishabh Pant (91) and Cheteshwar Pujara (73) have been India's other major contributors.
For England, Dom Bess was the most successful bowler with 4 for 77 while James Anderson (2/46), Jofra Archer (2/75) and Jack Leach (2/105) got two wickets each.
Local player Washington missed out on what would have been a well-deserved maiden Test hundred after hitting 12 fours and two fine sixes and sharing an invaluable partnership of 80 runs for the seventh wicket.
Washington was left stranded when Jasprit Bumrah was superbly caught in the slips by Ben Stokes to give Anderson his second wicket and signal the end of India's innings.