The Canadians now refused entry to Russia include Prime Minister Stephen Harper's foreign policy advisor Christine Hogan, parliament speaker Andrew Sheer and journalist turned politician Chrystia Freeland, the foreign ministry said in a statement.
"This step has been taken as a reaction to the unacceptable actions of the Canadian side which have brought serious damage to bilateral relations," it said in a statement.
It accused Canada of ignoring the referendum results where Crimea voted to become part of Russia and instead supporting the "current illegitimate regime in Kiev" which took power following the overthrow of President Viktor Yanukovych.
Others banned from entering Russia include Wayne Wouters, Canada's top civil servant, the leader of the government in parliament, Peter Van Loan, as well as Paul Grod, the head of the Ukrainian Canadian Congress which represents the Canadian diaspora.
The sanctions came after Harper at the weekend become the most senior world statesman to visit Kiev after the fall of Yanukovych.
Canada, with the world's third-largest population of ethnic Ukrainians, was the first Western power to recognise the ex-Soviet state's independence in 1991.