Star midfielder Scott Pendlebury will again take the vice-captaincy, while Luke Ball and reigning Copeland Trophy winner Dayne Beams will act as dual deputy vice-captains.
Collingwood coach Nathan Buckley said the selection was a relatively simple process, reflecting the high standards set by the four players around the club.
"They're all fantastic positive examples about how to go about your footy, they're great teammates, they're great footballers and we're looking forward to their influence throughout the group," Buckley said.
"These four guys lead the way for their teammates and they'll be expected to drive this playing group to great things this season.
"[They] were clearly seen as the guys that the group looked up to and wanted to follow."
Maxwell enters his fifth season in the role, while Pendlebury has been vice-captain since 2009.
At 25, Pendlebury is seen as the obvious successor to Maxwell when the incumbent leader hands over the reins.
Maxwell said he would be more than willing to step aside if the team decided it needed a change in the future.
"If at any stage my influence drops off, or if my teammates or the club feel that there's someone better to lead the club, then I'll step aside and be the first one to stick my hand out and shake their hand," Maxwell said.
But Maxwell said there is no formal handover process in place.
While some clubs have opted to adopt large leadership groups, Buckley said Maxwell, Pendlebury, Ball and Beams were the clear standouts.
"These four guys clearly stood out, but there are other leaders in the group and we'll be calling upon them throughout the year," Buckley said.
Travis Cloke, Dale Thomas, Heath Shaw, Harry O'Brien and Jarryd Blair were included in the leadership group in 2012, but do not feature this year.
Maxwell pointed to the development of the club's younger players, including Beams, Blair and Steele Sidebottom, as critical if the Magpies are to continue their strong leadership customs.
"We want to make sure that when the older players do leave we leave a legacy for guys to step up and take over that leadership."
Ben Guthrie is a reporter for AFL.com.au. Follow him on Twitter- @AFL_BenGuthrie