McMahon joins fellow Commonwealth Games gold medallist Kurt Fearnley in being appointed to the leadership positions.
They are joined by Chef de Mission Petria Thomas, and team performance general manager, Tim Mahon.
“They are already great ambassadors for Australian sport and the team in Birmingham will certainly benefit from their leadership,” Thomas said of the pair's selection.
“Sharelle and Kurt both bring an enormous amount of experience and insight and they are both great Australian champions that our team will greatly benefit from.
“The respect they command within the Australian sporting community is immense and as a collective our team executive can help establish the standards and expectations for the way the team conducts itself.”
McMahon competed at four Commonwealth Games as an athlete, while she was the youngest member of the netball side at the 1998 event in Kuala Lumpur.
“For me, during my career, it was a tournament that I always loved, so it will be exciting to be back,” McMahon said.
“Helping the entire team to have a great experience, both in terms of performance, but I always loved the feel of the Commonwealth Games so I’m really excited about being part of creating something special for everyone who’s involved.”
The Birmingham 2022 Commonwealth Games will take place from July 27 to August 7 with Australia expected to take their largest ever team.