After less than a year in office as Speaker for the Senate, on February 8, 1995, Roméo LeBlanc was appointed Canada's 25th Governor General of Canada, a position he held until October, 1999.  He was the first Acadian and first Maritimer to serve.  He and his wife, Diana Fowler LeBlanc, whom he married in 1994, undertook a vigorous schedule of activities that took them across Canada and abroad.

Within Canada, he focussed his attention on teaching Canadians about themselves; the history of Canada and the stories of the people who had created it were at the heart of his speeches.  With regard to Aboriginal people, he stated, " … that all of Canada owed them a debt that is four centuries old. It is their turn to become full partners in developing an even greater Canada." He continued: "And the reconciliation required may be less a matter of legal texts than of attitudes of the heart." Speech on the occasion of the presentation of the 1996 Native Role Models, February 23, 1996.

When receiving foreign dignitaries or representing Canada abroad, he emphasized the efforts that Canadians made to build an identity that reflected our core beliefs, the rule of law, and the need to strive for a caring and just society.  He also saw Canada as a country that would celebrate, rather than fear, diversity.  As an Acadian, he was convinced that Canadian institutions and values allowed individuals to preserve distinctive cultural heritage as part of a vibrant and united nation. 

During the four years he was Governor General, Roméo LeBlanc visited many countries, including the Czech Republic, the Netherlands, France, Guyana and Mexico.  He was the first Canadian Governor General to make a state visit to India and Pakistan.  In 1999, he was again the first Canadian Governor General to make a state visit to Africa, where he visited Senegal, the Côte d'Ivoire, Tanzania, and Mali.  That year, he also represented Canada at the funeral of King Hussan II of Morocco.