McGee has been recruited by the charity to build on the work of his predecessor Delroy Corinaldi.
Corinaldi was the charity’s first external affairs director and McGee will be reinforcing his efforts to make the charity more prominent in public affairs, overseeing an eight-strong external affairs department.
McGee was head of policy and external affairs at the Government-backed Money Advice Service until June 2012.
McGee's previous jobs include head of corporate affairs for insurer Aegon UK. He has also worked at the Treasury, Bank of England and the Personal Investment Authority, which was folded into the Financial Services Authority.
He said: "I am looking forward to representing the interests of individuals and families with problem debt and to advancing free debt service across the UK."
Corinaldi, who decided to move from the charity earlier this year, is currently considering new challenges but continues to work with the Financial Inclusion Centre thinktank.