Following discussions between Prime Minister Scott Morrison, Defence Minister Peter Dutton, and their Ukrainian counterparts, an additional $21 million worth of Australian Defence Force stock will seek to meet priority requests from Ukraine, the government announced on Sunday morning.
It comes on top of $70 million in military assistance Australia has already provided.
Australians who want to support those fleeing Ukraine will be able to make tax deductible donations to approved organisations supporting refugees in Poland, Romania, Slovakia and Hungary.
Ukrainians fleeing the conflict who have arrived in Australia will also be able to apply for a three-year temporary humanitarian visa.
Australia will donate at least 70,000 tonnes of thermal coal for Ukraine's power stations and withhold bauxite, used to make aluminium, from Russia.
An additional $30 million in humanitarian assistance will focus on protecting displaced women and children and addressing food shortages.
Australian Council for International Development CEO Marc Purcell said NGOs would work with government on delivering the assistance through the Australian Humanitarian Partnership.
"This is a critical intervention for the Ukrainian people in their hour of need and a demonstration of solidarity with their plight," he said.
The aid announcement comes after China's Vice Foreign Minister Le Yucheng warned against the unimaginable consequences of forcing a major nuclear power "into a corner".
Mr Le told a Beijing security forum on Saturday the North Atlantic Treaty Organisation should also avoid expanding further towards Russia.
He said the sanctions against the country are "getting more and more outrageous" and will only harm ordinary citizens and the global economy.
"History has proven time and again that sanctions cannot solve problems," Mr Le said.
Australia is not a member of NATO but allies including the United States and United Kingdom are.
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