The Bombers 18.13 (121) defeated the Magpies 13.9 (87) to notch their 11th win of the season and end the Pies' three-match winning streak.
A stunning first quarter from Essendon, which was not only its best first quarter for the season, but the best opening term from any team in 2004, set up the victory.
But after half-time, the Magpies showed plenty of grit for the rest of the match.
Collingwood coach Michael Malthouse said his side lacked intensity in the first term, but he was content with the character shown by his players after quarter-time.
"We played poorly. They played well and as a consequence you find yourself seven goals down (at quarter-time), but I was very pleased with the attitude and the effort to redeem some of the areas that we were poor and the boys hung in there," Malthouse said post-match.
"I thought we hung in there long enough against a side that was pretty desperate to make the eight.
"It's very easy to drop off (and) give a big lead like that. You can get a 10 to 12 goal blow-out and that's going to happen to sides that really fall off the pace at the end of the year, particularly against sides who aspire for the top eight."
Collingwood stalwart Scott Burns was outstanding for the Pies with three goals, while Brodie Holland was crucial with two majors and 21 touches. Shane O'Bree was the Magpies' leading ball-winner with 28 touches.
Ruckman/key forward Josh Fraser was also another fine player with 20 disposals and 11 marks, while defender James Clement gained praise from Malthouse for his performance down back and his ability to take the field after suffering a broken jaw last round.
"I thought it was an exceptional effort for Jimmy to get out there. It really was," Malthouse said.
Essendon opened the match with nine goals to two to lead by 40 points at quarter-time.
The Bombers booted three goals to zip, before Burns broke the Magpies' drought at the nine-minute mark. Essendon then piled on six of the remaining seven goals, as Tarkyn Lockyer was the only other goalkicker for the Pies before quarter-time.
But Essendon's goalkicking feast eased, as the Magpies outscored the Bombers with three goals to two in the second term, which reduced the margin to 35 points at half-time.
Collingwood continued to have the edge in the third quarter, when it added five goals to three, to trail by 24 points at three quarter-time.
This was despite the Bombers leading by 43 points at the 22-minute mark, which was their biggest lead of the match. But the Maggies booted three goals in six minutes, which included Burns' third at the 31-minute mark, to set up a fascinating final term.
And it proved that way, when the Pies kicked three of the opening four goals to get within 15 points at the 21-minute mark. But when Essendon answered with three in three minutes, it was out of Collingwood's reach.
On top of the loss, nominated rookie Nick Maxwell suffered a hamstring injury and Malthouse added that his future at the club would be known at the end of the season.
"We've got to make a decision on him now. (We'll have to) drop him off or put him on the list and that won't be done until the end of the year," Malthouse said.
Essendon: 9.2, 11.5, 14.8, 18.13 (121)
Collingwood: 2.4, 5.6, 10.8, 13.9 (87)
Goals: Essendon: Hille 4, Hird 3, Lucas, Watson, Dyson 2, J Johnson, Lloyd, Richards, McVeigh, Murphy.
Collingwood: Burns 3, Davis, Holland, Tarrant 2, Lockyer, Fraser, Lonie, King.
Best: Essendon: McPhee, Hird, Peverill, Hille, Stanton, Solomon.
Collingwood: Fraser, Holland, Burns, Woewodin, O'Bree, Licuria.
Injuries: Essendon: None
Collingwood: Maxwell (hamstring)
Changes: Essendon: Welsh (knee) replaced in selected side by Mark Mercuri
Collingwood: J Cloke (hamstring/thigh) replaced in selected side by McGough
Reports: None
Umpires: Allen, Ellis, McInerney
Crowd: 52,983 at the MCG