Small forward Jamie Elliott kicked five goals, including two in the last term, as the Magpies stormed back from 10 points down at the last change to win 17.15 (117) to 15.10 (100) in front of a crowd of 84,247.
As well as his own contribution on the scoreboard, Elliott dished a handball to Steele Sidebottom that set up the sealer with less than a minute to play, with Scott Pendlebury ramming home another major in the final seconds.
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The Magpies had seemed in big trouble early as Carlton's Andrew Walker kicked the first three goals of the match and Collingwood ruckman Darren Jolly went down with a rib injury in the opening minutes.
Jolly returned briefly to the field at the start of the second quarter but was soon subbed out, meaning key forward recruit Quinten Lynch had to spend most of the day in the ruck.
He was thrashed in the hitouts by Carlton's Matthew Kreuzer but worked valiantly at ground level, picking up 24 disposals and six clearances.
It also meant Travis Cloke, who was kept goal-less by Michael Jamison, had to play largely a lone hand as a marking target in attack.
But with Cloke failing to fire, Elliott stepped into the breach beautifully while small midfielder Jarryd Blair also chipped in with two goals.
As in last year's two clashes between these sides, Carlton's small forwards were very dangerous and looked set to prove match winners, with Chris Yarran and Jeff Garlett kicking three goals each.
Together with Walker's early haul and strong midfield showings by Marc Murphy and Chris Judd, it was enough to help Carlton lead for most of the day.
But goals to Magpies Ben Sinclair, Elliott and Blair in the first eight minutes of the last term gave Collingwood a 10-point lead.
And despite Garlett responding with a sensational snap from outside 50m to narrow the gap to less than a kick, they never gave up the lead.
Heath Shaw, Dane Swan, Sidebottom, Pendlebury and recruit Sam Dwyer were all important midfield contributors for the Magpies.
Collingwood 3.3 5.5 10.10 17.15 (117)
Carlton 3.0 7.3 12.8 15.10 (100)
Goals - Collingwood: Elliot 5, Sinclair 2, Blair 2, Pendlebury 2, Dwyer, Clarke, Shaw, Goldsack, Swan, Sidebottom
Carlton: Walker 3, Yarran 3, Garlett 3, Simpson, Bell, Rowe, Murphy, Lucas, Henderson
Best - Collingwood: Elliot, Shaw, Clarke, Dwyer, O'Brien
Carlton: Murphy, Yarran, Garlett, Judd, Gibbs
Injuries - Collingwood: Jolly (ribs)
Carlton: Nil
Substitutes - Collingwood: Darren Jolly (ribs) subbed out for Paul Seedsman in the second quarter
Carlton: Jeremy Laidler subbed out for Brock McLean in the fourth quarter
Reports: Nil
Umpires: Meredith, Jeffery, McInerney
Official crowd: 84,247 at the MCG
