In reply, West Indies were 34 for one at stumps Monday, trailing India by 212 runs.
Lendl Simmons was the lone West Indian wicket to fall in the post tea session. Adrian Barath was at the crease on 26 at close of play and giving him company was Ramnaresh Sarwan (2).
Ishant Sharma turned out to be the lone successful bowler for India with figures of one for eight.
Earlier, captain Mahendra Singh Dhoni`s decision to bat first at a two-paced Sabina Park pitch misfired as India suffered a top-order collapse before Raina (82) and Harbhajan (70) joined hands to resurrect the innings with a belligerent 144-run seventh wicket stand.
Raina and Harbhajan took the attack to the opposition during their 168-ball partnership to rescue India`s sinking ship after they were reduced to 85 for six at one stage.
The glorious seventh-wicket stand between the duo was the only silver lining in India`s innings as the visitors lost their last four wickets for a mere 15 runs.
For West Indies, the pace duo of Fidel Edwards (4 for 56) and Ravi Rampaul (3 for 59) shared seven wickets between them but it was young leg-spinner Devendra Bishoo (3 for 75), who impressed the most with his three-wicket haul and two outstanding catches.
Sent into bowl, Rampaul gave a dream start to the home team removing both the Indian openers -- debutant Abhinav Mukund (11) and Murali Vijay (8) -- within the first 12 overs.
Then it was Bishoo`s turn to stun the visitors with the prized wickets of VVS Laxman (12) and Rahul Dravid (40) on either side of the lunch.
As if this was not enough, Bishoo also claimed the vital wicket of India skipper Mahendra Singh Dhoni, who was out for his fifth duck in Test cricket, to register three scalps for 11 runs off his first 20 deliveries in the match.
But that was all the young leg-spinner could manage on the day before he was taken to cleaners by Raina and Harbhajan, who scored a mammoth 60 runs off Bishoo`s next seven overs.
Raina alone scored 40 runs off Bishoo with eight fours before he once again made his presence felt in the match but this time on the field.
After India had recovered to be 231 for six in the final session, Bishoo came up with a stunning catch to break the dangerous-looking stand between Raina and Harbhajan.
He ran from the deep and dived full length to his left to catch Harbhajan`s mistimed hook off Edwards.
Bishoo later brought the lid on the Indian innings by taking Raina`s catch at the square-leg boundary off Rampaul`s bowling.
Earlier, India`s top-order batsmen found it difficult to come to terms with the tricky pitch on an extremely hot day as they lost both their openers -- young Murali Vijay (8) and debutant Abhinav Mukund (11) -- as well as middle-order mainstay Laxman (12) and another debutant Virat Kohli (4) in the 25.3 overs of the pre-lunch session.
The home team tasted its first success as early as in the fourth over when Vijay drove one straight to Bishoo at point off Rampaul.
Mukund showed good judgment of his off-stump but looked ungainly while trying to play the short-pitched deliveries.
His tendency to play away from his body proved costly when an inside edge off Rampaul took his leg-stump out of the socket.
Laxman then joined Rahul Dravid (40) at the score 30 for two after 11 overs as the visitors decided to hold back another debutant Virat Kohli.
For Laxman, it was only the seventh time during his distinguished career when he batted at the number four position.
Laxman was distinctly lucky when he edged the very first delivery he faced from Darren Sammy, but the ball fell short of the first slip.
The stylish Hyderabadi batsman got another lifeline in the 20th over at the personal score of five when Rampaul dropped a difficult chance at mid-on off Edwards.
But Laxman`s luck ran out when Bishoo dismissed him with his first delivery.
Laxman was caught at the slip by Sammy as he went forward to a tossed up leg-break from Bishoo, which spun and took the edge.
New man in Kohli opened his account in Test cricket in style as he flicked Edwards down to fine leg boundary.
But the West Indies pacer had his revenge in the next over when Kohli edged one to wicket-keeper Carlton Baugh to draw
The ever-reliable Rahul Dravid looked rusty initially but later his footwork improved and he played several delightful strokes before falling prey to Bishoo in the slip soon after lunch.
Dravid`s eyes lit up at a tossed up Bishoo delivery and he went for a mighty heave, only to find the ball spin and take the edge to Sammy in the slips.
Indian skipper Mahendra Singh Dhoni (0) did little justice to his reputation as he became Bishoo`s third victim soon, caught by Lendl Simmons at gully.
But then came in Harbhajan, who used his long handle to great effect and hit Bishoo for three fours off the first six deliveries he faced from the leg-spinner. The fiery Indian off-spinner meted out the same treatment to Edwards.
On the other hand, Raina started cautiously as he was subjected to a fair degree of short-pitched stuff by the West Indian bowlers.
But the young left-hander was up for the task as he showed great maturity in dealing with the short stuff.
The savage hitting of the pair quickly took Bishoo out of the attack as 150 runs came from the afternoon session.
Harbhajan completed his half century from only 45 deliveries with the help of nine fours.
The dominance of the duo can be gauged from the fact that they took just 120 deliveries in notching up their 100-run seventh-wicket stand.
But West Indies gathered their wits at tea break and pressed into service their frontline bowlers from both ends on resumption, which promptly paid dividends.
Edwards kept two fielders in the deep and bowled a short delivery at Harbhajan, who mishit one to a diving Bishoo. He made his 70 off 74 balls and hit 10 fours and a six.
Raina then witnessed Praveen Kumar (4) and Amit Mishra (6) quickly before he became the last man to depart. His 82 came off 115 balls and was studded with 15 hits to the fence.