The prime minister's plane arrived in Rotterdam, the Netherlands, late Friday for a trip that will include talks early next week on nuclear safety.
He will make a quick trip to Kiev Saturday.
Canada has joined other G7 leaders in their condemnation of Russia's military action against Ukraine and last Sunday's referendum results, which have been denounced as a violation of international law.
Harper's visit to Kiev — where he will meet with Ukraine's Interim Prime Minister Arseniy Yatsenyuk — will be further "expression of Canada's principled stand on Ukraine," said the prime minister's director of communications, Jason MacDonald in an interview with CBC News on Thursday.
Harper will use Saturday's photo op with Yatsenyuk as an opportunity to show that Canada condemns "Russia's illegal occupation of Crimea" and continues to stand in solidarity with the people of Ukraine as they move to build a democratic country with presidential elections set for May 25.
Foreign Affairs Minister John Baird, who was in Kiev's Independence Square amid protests last month, will be accompanying Harper on his visit to Ukraine.
The opposition New Democrats and Liberals both told CBC News on Thursday they were not invited to take part in the prime minister's visit to Ukraine.
Canada welcomes latest U.S. sanctions
While Ukraine's interim prime minister has left his country to solicit the support of other world leaders during the crisis in his country, no G7 leader has set foot in Ukraine amid the political unrest.
The significance of Harper's visit did not escape Ukraine's Ambassador to Canada Vadym Prystaiko.
"This visit is a very particular one and the significance of this visit is that Canada has taken the leadership on assistance to Ukraine," Prystaiko said Thursday during an interview with CBC News.
Canada's aid to Ukraine as well as the sanctions it has imposed on Russia have been in lockstep with similar announcements made by the international community.
U.S. President Barack Obama announced further sanctions against Russia on Thursday, which prompted Putin to retaliate by barring a number of U.S. government officials from travelling to Russia, including House Speaker John Boehner and Senate Majority Leader Harry Reid.
Obama announced economic sanctions targeting members of Putin's inner circle as well as a Russian bank that provides them support.
"Canada welcomes the sanctions announced by the U.S administration," MacDonald told CBC News on Thursday.
Canada has announced $220 million in financial assistance to Ukraine, most of it conditional on the establishment of a broader package by the International Monetary Fund.
The Canadian government has also imposed economic sanctions and travel bans on 45 Ukrainian and Russian officials.
Further Canadian assistance
The ambassador said he expected Harper would make further announcements "as soon as he arrives" in Kiev on Saturday.
Prystaiko said they "are working on different projects," some that may require technical assistance, and some that may need financial support.
The ambassador said money is good but Canada could lend its expertise in a wide range of fields.
Prystaiko said he would expect Harper to send a team of election observers in time for Ukraine's presidential elections at the end of May, as Canada has been known to do.
"I would expect that these elections, which will happen on May 25, will have some Canadian observers to help us with observation," Prystaiko said.
The ambassador said Canada could also help Ukraine rebuild its policing forces, or help with their hospitals, which are struggling to treat "hundreds of people."
Joan DeBardeleben, a political science professor at Carleton University in Ottawa and the author of numerous books dealing with Russian politics, said there is definitely more Canada can do to help restore stability in the country.
In particular, DeBardeleben said Canada could offer advice to Ukraine's government on ways to reach out to the Russian minority in the country.
"In terms of developing mechanisms and vehicles of social inclusion for minorities. It's something we have a lot of experience with in terms of multiculturalism."
"The legitimacy of the new interim government in Ukraine will depend very heavily on whether it succeeds in that task," DeBardeleben said.
Expelling Russia from G8?
Harper will travel from Ukraine to the Netherlands for bilateral meetings with his Dutch counterpart, the Prime Minister of the Netherlands Mark Rutte.
Here, Harper will be accompanied by Industry Minister James Moore.
While in The Hague, Harper will attend the third Nuclear Security Summit, which will be hosted by Rutte.
Prystaiko said Ukraine's interim prime minister would see Harper again during the summit, hoping to "squeeze in as much as possible in this short visit."
An emergency meeting of the G7 will be hosted by the U.S. around the summit to consider a further response to Russia's move to annex Ukraine's Crimea region.
The G7 includes the U.S., Germany, Britain, Canada, France, Japan and Italy.
The European Union was also invited to take part in the talks.
British Prime Minister David Cameron said this week that the leaders should discuss expelling Russia from the G8, a move Canada has said the group ought to consider.
Baird also raised the topic this week saying while it was up to the leaders to make that decision, where Canada was concerned, Russia could "absolutely" get expelled from the G8.
Harper first drew a line in the sand with Putin, during a meeting of the G8 in Northern Ireland last summer, when he publicly denounced Putin for his support of Syrian President Bashar al-Assad's regime.
"This is G7 plus one," Harper said at the time.
Following the Nuclear Security Summit and the emergency meeting of the G7 leaders, Harper will travel to Germany where he will meet with German Chancellor Angela Merkel to discuss a number of bilateral issues.
A discussion on the next steps in co-ordinating a response to the unrest in Ukraine will top Harper's agenda, along with Europe's economy, and the Canada-EU trade agreement.
International Trade Minister Ed Fast will accompany Harper for the last leg of his visit to Europe.
Source: CBC News