Balme, who was at the Magpies from 1998-2006, returns to the club after a successful eight-year stint at Geelong.
The Magpies approached Balme last week about filling the vacant role and the offer, according to the Cats' former footy boss, was too good to refuse.
Balme leaves Geelong with the club's blessing and, as the contracts of Cats' senior officials roll over year by year, there was no need to sort out any compensation for his departure.
He will remain at the Cats until the completion of this month's NAB AFL Draft.
"I'm very ambivalent with the whole Geelong-Collingwood thing," Balme said on Monday.
"I'm sure once I get there, I'll see it as a great idea. But right now I can only really think about Geelong.
"I'm really excited about the new opportunity, but I'm still wedded to this place right at the minute.
"But it was too good an opportunity to miss. Whilst I don't want to leave this place, I think it's a great opportunity."
Balme said he was looking forward to working closely with Magpies coach Nathan Buckley.
"I've known 'Bucks' for a long time and he is someone I have the highest personal and professional regard for," Balme said.
"We share a lot of common ground in terms of our thinking on the game, the list is in a pretty healthy position and to take on the challenge of building something substantial and, hopefully, successful with him is of real appeal."
Steve Hocking will step up as Geelong's football manager after spending the past year as commercial operations manager.
CEO Brian Cook said Balme's decision to join Collingwood did not come as a shock to the club.
"We were not surprised that Collingwood approached Neil, and to his credit he has kept us up to date throughout those discussions," he said.
"This has allowed for a smooth transition to Steve, and it has also meant that we can start to formulate a plan to replace Steve as GM of commercial.
"The transition to Steve will be made much simpler by the fact that he has been so involved in our operations at all levels for so long."
Cook said Balme's influence was most pronounced in the support he provided coaches Mark Thompson and Chris Scott, as well as his role in providing the necessary support for the club's player leadership group.
"I've seen him as a wonderful relationship builder. Someone who calms the waters and someone who does provide the glue," Cook said.
"And he's someone who's good to be with."
Hocking was glowing in his praise of Balme, whom he worked closely with from 2007-2014.
"From Neil's point of view, relationship building has been absolutely exceptional," Hocking said.
"The external work he's done through the media. The presence that he's provided the Geelong Football Club, through the Melbourne and national markets, has been super impressive."