The Magpies trailed for much of the match and it took a late goal from Leon Davis to put them in front and give them the win, 12.14 (86) to 12.13 (85).
But it wasn't decided until the final second of the game.
Melbourne was pressing hard and had its chance when Rohan Bail, playing just his second game, bombed the ball to the goal square.
Forward Ricky Petterd, so important all day with four goals, had what could have been a mark knocked from his fingertips.
Magpie Steele Sidebottom helped spoil Petterd's attempt, and the siren sounded as players converged on the ball.
The Demons were unable to scrounge a score of any kind to salvage any points from the match.
And as the better team on the day, they probably deserved to, although coach Dean Bailey knew his side blew its chances.
"That's why the game is never, ever won until the siren goes so you've got to push and push until the last second because you never know what might happen," Bailey said after the match.
"We had our chances in the last two minutes when we went inside 50 a couple of times and we just unfortunately didn't take those chances."
While the match never rose to great heights skill-wise, it was compelling viewing as Melbourne served it right up to Collingwood - a week after its 56-point loss to Hawthorn.
Collingwood entered the game practically unbackable after knocking off pre-season flyer the Western Bulldogs in round one.
From the opening bounce, the Demons showed far more intent than their forgettable first-up display.
They led by 15 points at quarter time - the biggest margin of the game - but couldn't find the knockout blow in the final minutes when they seemingly had the Magpies on the ropes.
Through quick attacking footy and controlled aggression, Bailey’s side dominated the inside-50 and contested possession counts.
Collingwood responded in the second, booting the first four goals of the term to jump to an 11-point advantage.
Late replacement Dayne Beams and Scott Pendlebury helped the Pies back into the contest, although they struggled to find a clear winner up forward. Losing defender Ben Johnson to what looked a serious knee injury didn’t help their cause.
The Demons refused to buckle however, with Jack Grimes and Aaron Davey providing plenty of run while their tall defenders again kept a close watch on the opposition’s danger men.
Petterd kicked a steadier for the Demons and when he added his third later in the quarter his side remained less than a kick behind at the long change.
The question was: would Melbourne surrender meekly after half time? The answer was no.
Collingwood was playing only in spurts, with Alan Didak, Travis Cloke and Paul Medhurst struggling to get into it, leaving Dale Thomas, Sidebottom and Sharrod Wellingham to provide the spark.
The Demons looked the better team and with 200-gamer Brad Green providing a target, should have led at the last break.
Inaccurate kicking for goal proved costly but three of the first four goals of the last term set up an 11-point lead 20 minutes into the final quarter.
Jack Anthony bobbed up for a goal and when Davis, who had been reasonably quiet to that stage, calmly slotted another with just under four minutes to play, the Pies were back in front.
The final seconds were heart-pounding stuff, but Malthouse’s team limped across the line.
"Did we deserve to win? Well, when there’s one point [the difference], there’s a victor that’s lucky and there’s a loser that’s unlucky and that’ll always be the cry," he said.
"We need to address the differences between how good we play and how poor we play.
"[But] I am not about to underestimate or understate how good Melbourne were today."
Collingwood 2.2 7.5 10.10 12.14 (86)
Melbourne 4.5 6.6 9.11 12.13 (85)
GOALS
Collingwood: Pendlebury 2, Lockyer 2, Davis 2, Anthony 2, Fraser, Cloke, Medhurst, Beams
Melbourne: Petterd 4, Green 3, Dunn 2, Bail, Newton, Bennell
BEST
Collingwood: Pendlebury, Davis, Beams, Maxwell, Sidebottom, Wellingham
Melbourne: Green, Petterd, Davey, Jamar, Moloney, Grimes, McKenzie
INJURIES
Collingwood: O'Bree (virus) replaced in selected side by Beams, Johnson (knee)
Melbourne: Spencer replaced in selected side by Bartram
Reports: Nil
Umpires: Hay, Wenn, Jeffery
Official crowd: 50,421 at the MCG
The views in this article are those of the author and not necessarily those of the club.