Canada is operating independently of NATO to provide additional military assistance that will help Ukraine defend itself from Russia.
The aid comes as Ukraine battles pro-Russian insurgents in its eastern region, part of a conflict beginning with the annexation of Kiev's Crimean peninsula that has triggered the worst dispute between the West and Moscow since the Cold War.
Defence Minister Rob Nicholson was in Kiev Monday for Canada's announcement, which will include sending Canadian soldiers to Ukraine to train that country's military police. It could also include training in battlefield medicine and security measures.
The aid stops short of providing lethal equipment such as weapons – something Kiev has long sought from North Atlantic Treaty Organization members.
A group of Canadian military police arrived in Ukraine Monday evening to begin training. The military would not provide exact numbers but said the contingent amounts to less than 10.
The Canadian government and Ukraine issued a declaration of intent Monday in Kiev which is not a legally binding treaty under national or international law but nevertheless a commitment to expand Canada's military cooperation with Kiev.
"Russia has flagrantly violated the territorial integrity of Ukraine and continues its efforts to intimidate and undermine the democratically elected government in Kiev," the declaration reads.
"Canada and Ukraine are committed to continue working together to strengthen the capacity of the Ukrainian government and its security forces to defend Ukraine's territorial integrity and its people," the agreement says.
"We declare our intent to continue working together to explore ways in which to build upon these gains, particularly as concerns defence capacity-building through the provision of general support training such as military police, medical and personal protective measures."
The Ukrainian government elected in October 2014 has made joining NATO a priority. NATO has conducted military training exercises in Ukraine with Ukrainian troops as recently as September 2014.
The long-planned exercise, codenamed Rapid Trident, near Lviv, Ukraine, took place more than 1,000 kilometres from the conflict in the country's eastern region.
The West blames Russian President Vladimir Putin for providing weapons, funds and fighters to fuel the fight with Ukraine.
In August, Canada donated non-lethal military supplies to Ukraine, including helmets, ballistic eyewear, protective vests, first aid kits, tents and sleeping bags.
In November, Canada announced further military gear for Kiev including 30,000 winter coats, 70,000 pairs of Gore-Tex boots, tactical communications gear, bomb disposal equipment, medical kits, night vision goggles and winterized kits to expand the capabilities of the Ukrainian Armed Forces.