He was a pupil at Ndamase High School, near Umtata before attending the Federal Theological Seminary in Alice where he became the local chairman of the South African Students' Organisation (SASO) where he was involved in the exploration of black and liberation theology and in developing programmes to assist communities with basic amenities such as dams, schools and clinics.
He became a minister of the Methodist Church of southern Africa (MCSA) in Empangeni, KwaZulu-Natal in 1978, a post he held until 1982.
At the Central Methodist Mission in Johannesburg, Mvume’s mediation and conflict resolution skills were in great demand during the preparation for the political transition in the late 'nineties.
He found himself having to be at the forefront of helping to reduce violence in order to create an atmosphere where elections could happen peacefully.
This led – in the years directly after the elections – to his playing a critical role in the disarmament of the African National Congress's (ANC) Self Defence Units and the Inkatha Freedom Party’s (IFP) Self Protection Units in the Eastern Areas of Johannesburg.
[4][5] In June 2010 he resigned from COPE after much in fighting among senior party leaders Mosiuoa Lekota and Mbhazima Shilowa.