Australia will send a further $26.5 million in military aid for Ukraine in the form of anti-armour weapons and ammunition.
Prime Minister Scott Morrison made the announcement on Friday as the first of 20 Bushmaster armoured vehicles, which include two ambulance variants, worth $50 million were loaded into C-17 Globemasters.
Mr Morrison says he couldn't go into further detail about the new package at the behest of Ukrainian officials and Australia's partners, but it included "capabilities that have proven critical on the battlefield so far".
"What it demonstrates is that our support continues and will continue," he said.
"I said they have our prayers, but they've also got our guns and ammunition. We have been able to redirect some of our supplies to the frontlines in Ukraine to ensure they can continue the fight."
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.
A Ukrainian flag is painted on either side alongside the words "United with Ukraine" stencilled in English and Ukrainian.
Defence Minister Peter Dutton said Australia will continue to provide what military assistance it can to Ukraine as forces continue to repel the Russian invasion.
"It is one of the world-leading vehicles and it provides protection to the crew that are on board," he told the Nine Network.
"It will be a big win for the Ukrainian forces in their attempts to stare down the barbaric efforts of the Russian forces."
It comes a day after Foreign Minister Marise Payne announced further sanctions against 67 Russian elites.
The sanctions have been extended to Deputy Prime Minister Dmitry Grigorenko and military official Colonel-General Mikhail Mizintsev, labelled the "Butcher of Mariupol", for attacks against buildings sheltering civilians.
The Kremlin retaliated overnight, announcing its own sanctions against 228 Australian government members and politicians including Mr Morrison and Mr Dutton.
But Mr Dutton said Australia would continue to stand with Ukraine again tyranny and autocrats.
"People have fought and died for the freedoms that we have in our country. We need to realise we just can't take for granted what we have - our system of democracy and freedom of speech," he said.
"These are values that dictators like Putin and Hitler and others will always be against. We need to stand up against them."
Meanwhile, the United Nations 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.
"Russia must pay a terrible and awful price for what they have done to Ukraine," he said.
"This was an important thing to do ... to send a very strong message that any others that would want to act in this authoritarian way on their neighbours - including right here in this region - that Australia will always stand up."
Senator Payne is in Brussels to meet with ministerial counterparts from other NATO countries and allies to discuss Russia's ongoing military assault.
But the foreign minister is not going to expel the Russian ambassador for the time being.
"Having a diplomatic path to discuss these issues can be very important," Senator Payne told Sydney radio 2GB.
"I'm also conscious that there are hundreds and hundreds of Australians in Russia, many of whom will potentially reach out to our embassy for consular support."
Labor has urged the government to expel all Russian diplomats, barring the ambassador, to hold the Kremlin accountable for reported atrocities.
with Reuters
