Archbishop Ndungane decided to enter the church during his three-year sentence on Robben Island as a political prisoner in the early 1960s. In 1975 Ndungane left South Africa for King's College London where he earned first a Bachelor of Divinity degree, then a Master of Divinity, concurrently working as a curate in London. He went on to serve as Bishop of Kimberley and Kuruman from 1991 to 1996, and subsequently served as Archbishop of Cape Town from 1996 to 2007.