Bushmaster vehicles and M777 howitzer guns were onboard a flight that departed from RAAF Base Amberley, near Ipswich, on Thursday.
The federal government will send 20 Bushmaster Protected Mobility Vehicles, and six M777 howitzers with ammunition, as part of its aid to the Eastern European nation.
More than $225 million in military assistance has been contributed by Australia.
Russia has declared its offensive in Ukraine a "special operation" to disarm the country and protect it from fascists, which it claims have infiltrated the government.
Ukraine denies the fascist allegation as baseless, labelling the war an unprovoked act of aggression.
Ukraine's Foreign Minister Dmytro Kuleba said strong Australian support for his country came from an understanding of the precedent the invasion could set for other countries.
"You understand if Russia succeeds in Ukraine it will inspire other countries in your part of the world to behave in a similar way," he told the ABC's 7.30 program on Thursday.
"You want us to succeed in order to prevent this pattern of aggressive warfare to be localised ... and not stretch to other parts of the globe, posing direct security to Australia."
Mr Kuleba said Australia's support had been the "biggest pleasant surprise" since Russia's invasion in late February.
"You cannot imagine how much we appreciate the fact that a country that is so far away from us, demonstrated this level of empathy and support to Ukraine," he said.
Russia has turned its heaviest firepower on Ukraine's east and south, after failing to take the capital Kyiv.
The new front is aimed at limiting Ukraine's access to the Black Sea, vital for its grain and metal exports, and linking Russian-controlled territory in the east to Crimea.
President Volodymyr Zelenskiy said the war had devastated hundreds of hospitals and medical facilities.
Doctors are without the medication needed to treat cancer or perform surgery.
"As of today Russian troops have destroyed or damaged nearly 400 healthcare institutions: hospitals, maternity wards, outpatient clinics," Mr Zelenskiy said on Thursday.
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