Lokesh Rahul then made the most of his inclusion in the final 11 in place of the injured Murali Vijay, reaching an unbeaten 75 as India closed the first day at 126 for one in reply.
Ashwin followed up his haul of seven for 83 in the final innings of the first Test a week earlier with five for 52 on a pitch offering turn and bounce from the very first session of play.
He became just the third Indian bowler to have five-wicket innings hauls in three consecutive Test matches after fellow spinners Bhagwat Chandrasekhar and current coach Anil Kumble.
“Going into any match I assess the batsmen in the opposition to see if I have dismissed them before,” said Ashwin after the day’s play.
“I then work on getting them out based on their strengths and weaknesses. It’s never as easy as it looks sometimes but it’s gone really well for me in the last two innings.”
Having ended the only substantial resistance from the home side when he dismissed Jermaine Blackwood for a run-a-ball 62 in the last over before the lunch interval, Ashwin added swiftly to his tally in the afternoon session, accounting for Marlon Samuels for 37 to a sharp catch at short-leg by Rahul and following up with the wickets of Shane Dowrich, Devendra Bishoo and captain Jason Holder in quick succession.
Blackwood and Samuels had put on 81 for the fourth wicket in the morning with Blackwood the dominant partner, stroking seven fours and four sixes in his counter-attacking innings.
But it was not enough as the clatter of wickets resumed after he was trapped LBW by Ashwin.
“Marlon (Samuels) encouraged me to just stay positive and play my natural game,” said Blackwood.
“I wanted to put the bowlers under some pressure. It was very disappointing to get out when I did, very emotional really. I just hope I can do even better in the second innings.”
WATCH: Jermaine Blackwood spoke to the Media after the 1st day of the 2nd Test vs India, https://t.co/4pUee0ZYQE— westindies (@westindies) July 31, 2016
Debutant Miguel Cummins heaved his way to an unbeaten 24 in an entertaining 38-run last-wicket stand with Shannon Gabriel before leg-spinner Amit Mishra ended the innings to put the seal on another efficient effort in the field by the visitors.
India were in control virtually from the start of the match after Holder’s decision to bat first on winning the toss as the West Indies slid to seven for three within 25 minutes of play.
Ishant Sharma removed Kraigg Brathwaite and Darren Bravo off successive deliveries in just his second over.
With a reputation of susceptibility to the short ball early in his innings clearly on the fast bowler’s mind, Brathwaite failed to negotiate a lifting delivery in Sharma’s second over and Cheteshwar Pujara held the simple catch at short-leg.
Bravo’s weakness outside the off-stump was then immediately capitalised upon, the left-hander failing to cover a full-length delivery properly for a delighted Indian captain Virat Kohli to take the catch at second slip.
Rajendra Chandrika, the other opener, then gave catching practice to Rahul in the slips as he guided a lifting delivery from Mohammed Shami unerringly into the hands of the fielder.
In stark contrast to the West Indian experience at the start of the match, the Indian top-order batting had things pretty much their own way in the final session of the day.
Rahul and Shikhar Dhawan put on 87 for the first wicket before Dhawan became Roston Chase’s first Test wicket, well caught by Bravo at short extra-cover for 27.
None of the other bowlers looked particularly threatening though and Rahul and Cheteshwar Pujara will resume on the second morning expecting to put India firmly in control in pursuit of a second win in a row at the start of the four-match series.