It comes after the Morrison government announced on Friday it will send a further $26.5 million in military aid for Ukraine in the form of anti-armour weapons and ammunition.
Foreign Minister Marise Payne also announced further sanctions against 67 Russian elites.
Opposition defence spokesman Brendan O'Connor said the party backed the government's response to the war.
"We support the lethal and non-lethal aid that's been provided … and indeed, I think the reconstruction of that city that's been under siege, clearly will need help from not just its European friends, but friends around the world," he told the ABC.
Mr O'Connor said he hoped the government would brief Labor on any new decisions it planned to make in offering assistance to Ukraine as it entered caretaker mode during the election campaign.
He said retaliatory sanctions imposed by Russia on more than 220 Australian parliamentarians were unsurprising.
"What we have done to date is to stand up for sovereignty, independence and democracy, and we had no choice but to do that," Mr O'Connor said.
The first of 20 Bushmaster armoured vehicles worth $50 million, including two ambulance variants, have been loaded into C-17 Globemasters.
"I said they have our prayers, but they've also got our guns and ammunition," Mr Morrison said.
The Bushmasters were painted olive green to suit the environment in Ukraine and will be fitted with radios, a global positioning system and additional bolt-on armour to increase their protection.
The personnel carriers provide protection against mines, artillery shrapnel and small arms fire.
Ukraine's ambassador to Australia Vasyl Myroshenychenko said the nation hoped to force Russia out and rebuild.
"Ukraine is going through very difficult times. The number of military and civilian casualties is staggering. The war crimes of the Russian military is appalling."
The United Nations has voted to suspend Russia from the UN Human Rights Council, citing "grave concern at the ongoing human rights and humanitarian crisis", before the Kremlin then quit the council.
Mr Morrison said it was an important move to ensure Russia continued to be held accountable for its invasion of Ukraine.
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