Matthews was educated at Bishop Strachan School in Toronto, and graduated with a Bachelor of Arts(Honours) degree from Trinity College, University of Toronto in 1976. She was the recipient of the North American Theological Fellowship from 1976 to 1979, and completed a Master of Divinity at Yale Divinity School and Berkeley Divinity School. She also holds a Master of Theology from Trinity College, Toronto, which she completed in 1987.
Matthews is considered to be a theological conservative and on the Anglo-Catholic wing of the Church. Matthews became a deacon in 1979 and was ordained to the priesthood in 1980. In 1992, she sat on the bishop"s court that convicted Fr James Ferry of disobedience.
She served as an educator and a parish priest until February 12, 1994, when she was ordained to the episcopate.
From 1994 to 1997 she was Suffragan (Assistant) Bishop of Toronto. Mathews began chairing the Primate’s Theological Commission in 1996 and was reelected in 2004.
She also chaired the Task Force on Alternate Episcopal Oversight. She was elected Bishop of Edmonton in 1997, and held the position until her resignation in 2007.
She was bishop-in-residence at Wycliffe College in Toronto, Ontario, from January to April 2008.
Matthews" handling of the February 2011 Christchurch earthquake damage to ChristChurch Cathedral earthquake recovery was criticised by a senior church member and was echoed by letters published in The Press.
