Pendlebury, a dual Collingwood best and fairest winner, will be joined in the club's 2014 leadership group by Maxwell, Travis Cloke, Luke Ball, Steele Sidebottom, Lachlan Keeffe, Nathan Brown and Clinton Young in a new-look eight-strong leadership group.
The move completes a remarkable sporting journey for the 26-year-old, who had accepted a basketball scholarship at the Australian Institute of Sport and looked set for a career shooting hoops.
Instead, a change of heart led to his drafting to Collingwood and a highly successful AFL career, which includes four consecutive All-Australian appearances in the past four seasons.
Pendlebury has long been touted as a successor to Maxwell, a five-year captain who led the club in their 2010 premiership year under former coach Mick Malthouse.
Coach Nathan Buckley, himself the Magpies' longest serving captain, made the announcement at a function in Melbourne's CBD on Wednesday night but the club will formally unveil the new leadership group at its Westpac Centre training base on Thursday.