At stumps, on the fourth day, West Indies - after Matthew Hoggard had reduced them to 15 for two - were 83 for three in their second innings, a deficit of 30 runs.
However, Chris Gayle was 52 not out and Shivnarine Chanderpaul, who had defied England with an unbeaten first innings 136 not out, was unbeaten on 16 having now gone more than 14 hours without being dismissed this series.
But England, already an unassailable 2-0 up, were the only side left in this match with a realistic chance of victory on the final day at the Riverside.
Collingwood's 128, his fifth Test hundred and second of the series after his 111 in the drawn opener at Lord's, was the centrepiece of England's first innings 400 all out.
The all-rounder, together with wicket-keeper Matt Prior (62) added 169 for the seventh wicket after England had been in trouble at 165 for six.
"I know it is an over-used term but this was a dream come true," Collingwood, 31, told reporters after stumps.
Looking ahead, he added: "We've spoken a lot about being ruthless and tomorrow (Tuesday) and taking the opportunities when they come and this is another opportunity for a hard-fought win.
Collingwood paid tribute to the hard-hitting Prior, saying: "When a guy like Matty Prior comes in, and takes the attack to the opposition, it's very easy to get carried along with him."
Tailender Ryan Sidebottom's 26 not out, with five boundaries, took England to 400 and gave them a first innings lead of 113.
Fast bowler Fidel Edwards led the West Indies attack with five for 112 from 23 overs.
England, shortly after tea, lost two wickets with their score on 369.
Collingwood inside edged a drive off Collymore (two for 116) off the last ball of the 94th over and next ball Durham team-mate Stephen Harmison holed out off Daren Powell, who took three for 89 in 32 overs.
West Indies sent in Devon Smith to open in place of out-of-form skipper Daren Ganga
But Smith was out nought, lbw to Hoggard's fifth ball.
Ganga, in at seven for one, avoided the embarrassment of a pair.
But on six he pushed at a delivery from Hoggard, England's sixth-most successful Test bowler of all-time, and was caught behind by Prior.
Left-arm spinner Monty Panesar ensured the collapse continued when his fourth ball saw Runako Morton play on.
But Gayle, whose first fifty of the series came in 63 balls with seven fours, and Chanderpaul held firm.
At lunch, England were 202 for six, still 85 behind, with Collingwood 35 not out and Prior unbeaten on 16.
Ganga turned to the off-spin of Marlon Samuels, primarily a batsman, as England moved closer to parity.
Collingwood, however, confidently swept Samuels for four before a similar shot from Prior off the same bowler went for six.
The century stand came up in 165 balls when Collingwood cut Samuels for four, the second fifty up in 70 balls as England, with the new ball looming, cashed in against the lesser bowlers.
West Indies had let England off the hook, with Samuels's five overs costing 35 runs.
Prior, who became the first England keeper to score a century on Test debut with 126 not out at Lord's, scythed the first delivery with the new ball, from Collymore, over the slips for four and next ball completed an 87-ball fifty in style by lofting the bowler over mid-wicket for six.
Collingwood pull off Edwards, his 13th four, saw him to a hundred in 149 balls.
West Indies conceded a wasteful 38 bowling extras compared to England's lone first innings no-ball from Collingwood.
England resumed Monday on 121 for four, with Andrew Strauss 72 not out.
Strauss had only added five to his overnight score when Edwards had the left-handed opener edging to wicket-keeper Denesh Ramdin.
His 77, which featured 11 fours, was Strauss's best Test score since his 116 against Pakistan at Headingley in August 2006.