Prime Minister Stephen Harper says six Russians and six people from Ukraine will face economic consequences for their part in helping Russia violate Ukrainian sovereignty.
The Russians being added to the list include military heavyweights such as Valery Vasilevich Gerasimov, Russia's Armed Forces chief of the general staff, and Igor Girkin, a member of the military's main intelligence directorate.
Ukrainians now facing sanctions include Olga Fedorovna Kovatidi, a member of the Russian Federation Council from the annexed Crimean region.
Harper says Russia's occupation of Ukraine and its provocative military actions remain a serious concern to the international community.
The United States and other countries have imposed similar sanctions against dozens of people.
Last week Moscow said it would retaliate by blacklisting an assortment of individual Canadians and U.S. citizens.
But Russian officials said they would not release the names of those on the list.