Gov.-Gen. David Johnston says the award will be presented to a member of Klein's family in Calgary on Tuesday.
Klein no longer makes public appearances as he is battling a form of dementia.
In a news release out of Ottawa, Johnston says Klein made "lasting contributions to the province of Alberta and to public life in Canada."
Johnston says Klein served three consecutive terms as mayor of Calgary, during which time the city hosted the 1988 Winter Olympics and created a legacy of sports facilities and municipal infrastructure.
He later rose to become Alberta's 12th premier, leading his province "with a common touch and broad appeal through an era of economic advancement, innovation and prosperity that ultimately resulted in the elimination of the province's deficit."