Colin Munro was born on 24 October 1946, son of Captain Frederick Bertram Munro and Jane Eliza Munro. He was educated at George Watson's College, Edinburgh and Edinburgh University, graduating in Modern Languages in 1968 (and later took an MA in International Studies from King's College, London in 2002). In 1967 he married Ehrengard Maria Heinrich, having two sons.
Munro began his career as Assistant Principal at the Board of Inland Revenue, 1968-69, but switched to the Diplomatic Service in 1969. His diplomatic career included the following posts: Foreign and Commonwealth Office (SW Pacific Department), 1969-71; Third, later Second, Secretary, Bonn [Germany], 1971-73; FCO (Commonwealth Co-ordination Department), 1973; Second, later First, Secretary, Kuala Lumpur [Malaysia], 1973-77; FCO (Defence Department), 1977-79; FCO, Private Secretary to Minister of State (Peter Blaker), 1979-80; Head of Chancery, Bucharest [Romania], 1981-82; FCO (Western European Department), 1983-84, Assistant Head of Department, 1985-87; Deputy Head of Mission, East Berlin, 1987-90; Consul General, Frankfurt, 1990-93; FCO (Head of OSCE, the Organisation for Security and Co-operation in Europe and Council of Europe Department), 1993-97; Ambassador to Republic of Croatia, 1997-2000; Deputy High Representative, Mostar [Bosnia and Hercegovina], 2001; Royal College of Defence Studies, 2002; UK Permanent Representative to OSCE, Vienna [Austria], 2003-07.