Just two points separated the sides midway through the third quarter before the Hawks piled on four unanswered goals in what turned out to be a knockout blow in front of 74,095 fans.
Giving stand-in coach Brendon Bolton a perfect 4-0 record, the Hawks cruised to the finish line in the final term to win 17.13 (115) to 13.8 (86), taking their season tally to 10-3.
Vote for your top three players from Collingwood's loss to Hawthorn in the Magpie Army Player of the Year Award.
It was their sixth consecutive win over the Magpies and their 11th win in the past 14 clashes between the sides, with Collingwood's last win against the reigning premier coming in the 2011 Preliminary Final.
Midfielder Brad Sewell, who was challenged by Hawthorn coach Brendon Bolton two weeks ago and again by teammate Sam Mitchell pre-match, was a star at the coalface.
In a brutal clash that suited his contested style, Sewell racked up 26 possessions (11 contested) and seven inside 50s, kicking an important goal out of congestion in the third quarter to start the Hawks' run.
"It was good to see 'Sewelly' put another one on the board – two in a row," Bolton said post-match.
"This is a brutal, tough competition and he was a little bit slow to get going, but we always knew he would.
"He's proud and determined and I think (the motivation) is more from within than external."
Important forward Luke Breust continued his outstanding season, kicking 4.0 to take his tally in 2014 to 35.4.
Captains Luke Hodge (26 possessions) and Scott Pendlebury (35) went head-to-head for long periods through the midfield in an entertaining battle that saw both stars lead their teams well.
Collingwood spearhead Travis Cloke also built on his strong form, kicking five goals opposed to Brian Lake, who returned from a calf injury and was exposed at times in the contest.
While the Hawks awoke from a low-key run that has still seen them bank four consecutive wins, the Magpies lost their second straight game and could be two games adrift of the top four by the end of the round.
Buckley said the contested ball differential in Hawthorn's favour (145-117) was "like water dripping on a stone...eventually it told".
"We presented well for most of the first three quarters, but I didn't like the way we played in the last quarter," he said.
"It was our intent.
"We were too slow with the ball from our back half, and there were a few structural things that we didn't adhere to that had been in place and worked for us.
"We need to be better than that."
Hawthorn had the better of a high-pressure start, controlling possession and forcing the Magpies into errors, but Buckley's men eventually settled.
Back-to-back goals in a minute from Breust gave Hawthorn an eight-point lead at the first break, with the Hawks' forwards looming as a major threat.
They stamped their authority early in the second term, with Jarryd Roughead getting on top of Jack Frost and Breust continuing to trouble Tom Langdon, who was substituted late in the second quarter with concussion and didn't return.
With Sewell a standout in the middle, the Hawks built a 21-point lead in the second term before Cloke enjoyed a purple patch.
The power forward took two contested marks opposed to Lake and converted his set shots, before kicking a third on Shaun Burgoyne as the half time siren sounded, cutting the margin to just nine points.
Midway through the third quarter, Pendlebury was penalised for what was a clear handball, leading to the Sewell goal that kick-started Hawthorn's game-breaking run.
Buckley made his way to the bench late in the third term and vented his frustration to ruckman Jarrod Witts, who was one of the few Magpies to lift in the fourth quarter.
"It was designed as a prickle," the coach said.
"It was designed to really challenge him and wake him up in some ways."
The Magpies face Carlton at the MCG in round 15 while the Hawks will look to notch their fifth consecutive win, against Gold Coast at Aurora Stadium.
Collingwood 3.1 6.4 9.7 13.8 (86)
Hawthorn 4.3 7.7 12.10 17.13 (115)
Goals - Collingwood: Cloke 5, Elliott 2, Witts 2, Young, Macaffer, Blair, Adams
Hawthorn: Breust 4, Roughead 3, Rioli 2, Schoenmakers 2, Ceglar, Sewell, Hill, Puopolo, Gunston, Smith
Best - Collingwood: Pendlebury, Cloke, Elliott, Swan, Young
Hawthorn: Sewell, Breust, Hodge, Birchall, Spangher, Ceglar
Injuries - Collingwood: Tom Langdon (concussion) replaced by Tim Broomhead in the third quarter.SUBSTITUTES
Hawthorn: Nil
Substitutes - Collingwood: Tim Broomhead replaced Tom Langdon in the third quarter
Hawthorn: David Hale replaced by Ben Ross at three-quarter time
Reports: Nil
Umpires: Hosking, Schmitt, Pannell
Official crowd: 74,095 at the MCG
