List of Canadian ambassadors to the European Union with the rank and status of Head of Mission.
| Ambassador | Start of Term | End of Term |
|---|---|---|
| Sydney David Pierce | March 17, 1960 | October 31, 1965 |
| Paul Tremblay | May 13, 1966 | February 16, 1970 |
| A. Randolph A. Gherson[1] | February 17, 1970 | January 28, 1971 |
| James Coningsby Langley | December 10, 1970 | June 28, 1975 |
| Marcel Cadieux[2] | March 27, 1975 | September 8, 1978 |
| Richard Marcus Tait | October 12, 1978 | September 9, 1982 |
| Jacques Gignac | September 22, 1982 | - |
| Robert K. Joyce[3] | November 15, 1985 | - |
| Craig Thomas MacDonald[1] | October 1986 | - |
| Daniel Albert Bernard Molgat | January 22, 1987 | September 23, 1987 |
| Gordon Scott Smith | 1991 | August 12, 1994 |
| Jacques Silva Roy | August 30, 1994 | - |
| Jean-Pierre Juneau | September 11, 1996 | - |
| James K. Bartleman | July 26, 2000 | - |
| Jeremy Kinsman[4] | August 1, 2002 | - |
| Ross Hornby[4] | June 14, 2006 | - |