The Bushmasters, which include two ambulance variants, will leave Brisbane for Europe on C-17 Globemasters on Friday morning.
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 carries 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 on Friday.
"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 lawmakers including Prime Minister Scott 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.
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.
The minister said she and senior DFAT officials had "consistently conveyed" their views to Russian ambassador Alexey Pavlovsky over his country's invasion.
"It's important to realise that … 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.
"It is hard to conceive how the decision can be made to allow these individuals to stay, given the sickening abuses being carried out by Russian forces," Labor leader Anthony Albanese said.
Senator Payne said it was a possibility that Russian President Vladimir Putin could be tried as a war criminal, with a reference made to the International Criminal Court for the "horrific list" of atrocities.
Mass graves have been found, civilian shelters targeted by Russian shelling, and rape as a weapon of war has been reported by Ukrainian women.
"We have offered specialised Australian personnel to assist the court with those investigations ... that is part of holding Russia to account," the minister said.
"It is important that we prosecute this case as strongly as possible. Australia is a very clear and determined supporter of that."
with Reuters
