The 2010 premiership player and Norm Smith medallist will head Nathan Buckley's eight-man leadership group that includes Maxwell, Luke Ball, Nathan Brown, Steele Sidebottom, Travis Cloke, Lachlan Keeffe and Clinton Young.
The announcement, which was made on Wednesday, pulls down the curtain on Maxwell's reign as Magpies skipper after replacing Scott Burns at the end of the 2008 season.
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"It's a tremendous honour and obviously a privilege," said the 26-year-old Pendlebury, who becomes just the fifth Collingwood skipper in the past 20 years.
"I'm following in the steps of a great Collingwood captain. Maxy' led the side to a premiership and will play more than 200 games in black and white but I think that when his record is judged the selfless culture he worked to create and is so passionate about will be among his finest achievements.
"As a leader he laid out a path so many of us are now following and I'm sure he will continue to guide the group this year.
"He is a leader, with or without a title. That’s the sort of person he is. He sees this as a great opportunity for growth."
Coach Buckley also paid tribute to the veteran Maxwell, who guided the club to premiership glory in 2010.
"He has lived the Collingwood values, brought them to life for his team-mates in a way that few could have," said Buckley, who is tipped to sign a new two-year deal with the Magpies.
"The fans see it in his play on match day but his team-mates, coaches and staff see it and feel it in action every day."