Western nations and Latin American neighbours have been increasingly critical of Venezuelan President Nicolas Maduro this year, accusing him of stamping on democracy and human rights.
Venezuela says foreign governments are trying to encourage a right-wing coup. On Saturday, it also expelled the Brazilian envoy.
Venezuela had already withdrawn its ambassador to Canada in protest over sanctions against the Maduro regime that Canada imposed in September.
In a statement, Freeland said the ambassador was no longer welcome in Canada and that Venezuela's charge d'affaires is persona non grata.
Venezuela's expulsion of the Canadian diplomat over the weekend, she said, was "typical of the Maduro regime, which has consistently undermined all efforts to restore democracy and to help the Venezuelan people.
"Canadians will not stand by as the Government of Venezuela robs its people of their fundamental democratic and human rights, and denies them access to basic humanitarian assistance," she said in the statement.
Canada in September, following a similar move by the United States, imposed targeted sanctions against 40 Venezuelan senior officials, including Maduro, to punish them for “anti-democratic behavior.” The ministers of defense and the interior as well as several Supreme Court judges were also among those targeted by the measures.
Canada is a member of the 12-nation Lima Group, which is trying to address the Venezuelan crisis and which next meets in Chile in January.