Employment Minister Jason Kenney said the observers are part of Canada's answer to Moscow's provocations, especially in Ukraine's restive east.
The mission won't telegraph where it goes in advance, said Kenney, but he did not rule out the possibility Canadian observers could find themselves working in the same region where pro-Russian gunmen seized government buildings in several eastern Ukrainian cities following Russia's annexation of the Crimean Peninsula.
Still, he said he's not worried about the Canadian presence antagonizing the Kremlin, which has engaged in tit-for-tat democratic expulsions with Canada in recent weeks.
"I hope that Moscow notices. We are doing this in part to send a message as with everything else we're doing in Ukraine," Kenney told a conference call Wednesday as Foreign Affairs Minister John Baird continues his travels through eastern Europe.
"It is not Canada that is provoking the Russian Federation. It's the Russian Federation that is provoking the democratic world by so obviously undermining the sovereignty of an independent member state of the United Nations," he continued.
"There seems to be a view in Moscow that Ukraine is not a sovereign country, that its sovereignty can be tampered with with impunity."
Kenney said one way Canada is showing its disagreement with Russia is to strongly support "free and fair" presidential elections in Ukraine.
"The government in Moscow continues with the laughable notion that Viktor Yanukovych is the president of Ukraine," he said.
"These elections will demonstrate that there's a new Ukrainian leadership with a democratic mandate and that's why it's important that we be on the ground."
Prime Minister Stephen Harper said Wednesday that the Canadian delegation is to include up to 338 people in an election observation mission.
"Canada is a world leader in helping to promote democracy and good governance in Ukraine," Harper said in a statement.
"The measures announced today will help ensure that the upcoming Ukrainian elections are free and fair and that democracy and governance are the cornerstones of the new government."
Another group of up to 150 observers and 12 parliamentarians will join a election-monitoring mission from the Organization for Security Co-operation in Europe.
The government has earmarked $11 million to cover the costs of the observers.
The election is scheduled for May 25 and comes amid growing concerns about separatist tensions in the eastern part of the country.
Harper said Canada wants to ensure that Ukrainians can freely choose a leader without coercion or intimidation.
Since 2004, Canada has sent hundreds of observers to five successive Ukrainian elections. The Ukrainian crisis has resonance in Canada, where about 1.2 million people claim Ukrainian descent.
The prime minister has taken a keen interest in Ukraine even before the latest crisis, making clear his support for democratic institutions there.
Last month, he made a whirlwind visit to Ukraine, where he met acting president Oleksandr Turchynov and Prime Minister Arseniy Yatsenyuk.
Russia officially annexed Crimea last month and there are worries that Moscow may have its sights on more of the country.
Harper has taken a hard line against Russian President Vladimir Putin, saying his regime is a threat to world peace.
The most recent move came Tuesday when Russia expelled a first secretary at the Canadian Embassy in Moscow, an apparent retaliation for the earlier expulsion of a Russian military attache from Ottawa.
Canada has also imposed a number of political and economic sanctions against senior officials and some institutions in Russia and Ukraine.
Harper has pledged support for efforts to stabilize the Ukrainian economy, and dispatched Baird on a tour of eastern European capitals to bolster a common front against Russia.
Baird was in the Czech Republic on Tuesday, went to Slovakia on Wednesday and ended his day in Warsaw. He is scheduled to go on to Latvia and Estonia as well.
Also on HuffPost