At lunch, Virat Kohli (32) and Ravichandran Ashwin (26) were the unbeaten batsmen and the home side were 376 for 6, only 15 runs short of avoiding the follow on and 214 runs behind the rivals' score of 590. After lunch, the duo looked to score runs and the total went past the 400 mark.
Tendulkar was racing imperiously to his landmark after resuming at his overnight 67 in a team score of 281 for 3 when his dream was shattered, albeit temporarily, by Ravi Rampaul bowling with the second new ball.
The veteran right-hander, who had mixed caution with aggression in a judicious mixture till then, reached out for a slightly wide ball and the attempted drive to the off ended safely in rival captain Darren Sammy's big hands at second slip to send the 15,000 strong crowd at the Wankhede Stadium into a stunned silence.
The 38-year-old iconic cricketer could scarcely believe how he had missed out again when so close to the target and departed dolefully as the West Indians celebrated wildly.
The visitors had earlier drawn early blood by packing off the other overnight batsman V V S Laxman (32) off the first ball he played this morning, through a catch at gully off Fidel Edwards.
The Caribbean team struck another major blow after Tendulkar's dismissal by packing off India captain Mahendra Singh Dhoni for 8. With only five sessions left, the match appears to be heading for a tame draw.
When play commenced this morning, all eyes were on Tendulkar who was approaching the landmark for which the nation had been waiting for more than eight months.
Tendulkar had slammed his 99th international hundred (111) against South Africa in a World Cup league match at Nagpur in March.
Tendulkar, who needed 33 runs to reach the milestone, looked well-poised to complete the unprecedented feat after 39 minutes this morning when disaster struck.
Overnight 67 not out off 133 balls, the batsman easily negotiated the new ball taken by Sammy as soon as play commenced and was cruising merrily towards his 52nd Test hundred, much to the delight of fans assembled inside the 33,000-capacity arena.
Tendulkar, whose brilliant innings was laced with eight fours and two sixes, faced 153 balls in his 219-minute knock. He faced 20 balls this morning and added 27 runs with the help of three fours and a six.
He had previously fallen in the 90s in the fourth and final Test at The Oval against England when he made 91 before getting out leg before to Tim Bresnan.
Tendulkar started positively and scored mostly through flicks as the West Indian pacers bowled at his pads.
He flicked Rampaul for a two and a four off his legs but then saw Laxman perish. But Virat Kohli was looking confident while Tendulkar at the other end played a straight-drive off Rampaul which streaked to the boundary line even before the bowler could stop in his run up.
Then came the over from Edwards that proved extremely fruitful as Tendulkar took 14 runs that included a classic front-foot off drive and the cut over third man for a six when the bowler pitched short and wide.
Kohli hit a four off Rampaul and then Tendulkar got the strike in the same over which proved to be his last as he reached for the ball to drive and ended up giving a catch to the slip cordon and departed, stunned.
Kohli was joined by captain Dhoni who lasted only 21 balls before he was bowled by Sammy. However, Kohli and Ashwin prevented further damage before the interval while also adding 45 runs and bringing the team closer to avoid the follow on.