Pickett starred in the first half and Bayley Fritsch kicked three late goals for the Demons in their 12.11 (83) to 11.9 (75) victory in front of 88,019 fans at the MCG on Monday.
But there is concern for Mihocek, who was taken to hospital after he was accidentally hurt in a tackle from Billy Frampton.
A premiership Pie, Mihocek was playing his first match against his former team when he went head-first into the turf in the second quarter.
Play was held up for almost 10 minutes before Mihocek was driven off the field, but in a positive sign, the 33-year-old was moving his arms and communicating with medical staff.
The first King's Birthday blockbuster and Big Freeze event since Neale Daniher's passing a fortnight ago was a cracker, with neither side leading by more than 16 points throughout.
There were seven lead changes - three in the final term - and Pickett wasted two brilliant chances to end the contest in the dying stages before nailing the third.
Pickett finished with 28 disposals, five clearances and three goals despite being well held for most of the second half, and was awarded the Neale Daniher Trophy.
Jack Steele (26 touches), Harvey Langford (27) and Tom Sparrow (23) also shone, Jake Lever and Max Gawn stood tall, and Harrison Petty kicked two goals.
Collingwood gun Nick Daicos starred with 35 disposals, six clearances and two goals, with brother Josh (30 touches) and Patrick Lipinski (28) also busy.
Melbourne (8-5) move back into the top six, while Collingwood (5-7-1), who lost vice-captain Brayden Maynard to a dislocated shoulder in the second term, sit just outside the wildcard finals places after a fourth loss in five matches.
After the rival teams ran through a joint banner in a tribute to Daniher, Pickett immediately made his presence felt by slotting the opening two goals.
He tallied 17 first-half disposals and traded blows with Daicos, who had 22 touches and two goals of his own before the main break.
Jordan De Goey also slotted two brilliant majors, helping Collingwood to a narrow lead at halftime - 6.3 to 5.7.
Controversy erupted in the third quarter when play was stopped by an umpire after Pickett had his foot stepped on and stayed on the ground.
Melbourne were in possession about 30 metres away when the whistle went, and received a free kick to restart play.
Kade Chandler laced out Petty, who kicked a goal as Pickett shook off the injury.
Collingwood kicked three goals to two for the term, and turned for home with a five-point advantage.
Inexperienced forward Buller outmarked Gawn at full-forward and goaled to give the Pies breathing space but Fritsch returned fire for the Dees.
Pickett (twice) and De Goey missed huge late chances at opposite ends in the dying stages before Melbourne's star man settled the contest.
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