Scott Morrison has pledged $70 million to buy military equipment and weapons for Ukraine as part of a coordinated Western effort to help its armed forces resist Russia's invasion.
The government is also putting around $35 million toward humanitarian support to help international organisations responding to Ukrainians fleeing the country and seeking asylum in neighbouring regions.
Mr Morrison announced on Sunday that Australia would help provide "lethal aid" to Ukraine by contributing funds to NATO to bolster weapons shipments into the country.
Today's announcement put a dollar figure on exactly how much Australia would pitch in.
"The overwhelming majority of that [$70 million] will be in the lethal category," Mr Morrison said.
"We are talking missiles, ammunition, we are talking supporting them in their defence of their own homeland in Ukraine."
But the Prime Minister said he would not go into any more specifics on the new support.
He also ratcheted up his verbal attacks on Russia, saying it should be utterly isolated by the international community.
"They have self-selected themselves as a pariah state. That's how they should be known all around the world. No-one should have anything to do with them."
But when asked if Russia should be kicked out of the G20 he was more reserved, stressing Australia and other member countries were still discussing the "sensitive" issue with Indonesia, which currently holds the G20 presidency.
Mr Morrison said the government was receiving around 100 visa applications from those in Ukraine a day, which were still being processed as a "top priority".
People wanting to come to Australia from Ukraine have been urged to apply for various visas on offer, instead of just the ones available to refugees.
"They're visa applications across the entire migration program so they offer temporary visas on skills, education visas, family reunion visas," he said.
"For some of those on temporary visas, their attention will be different, they want to come to Australia for a period of time and I have no doubt they will want to return to their home country."
Australians again urged not to join fight
The government has ruled out sending troops over to fight in the war but has already committed to sending non-military equipment and medical supplies.
Mr Morrison once again urged people not to travel to Ukraine and join the fighting, saying it was still unclear what the legal position would be for people who chose to go.
It is currently illegal for Australians to join in foreign conflicts unless they are members of an official foreign army.
The head of the Ukrainian Council of NSW has said while the council appreciates Australia's support, people with no military training going to join the fight would be a "suicide mission".
Mr Morrison said that description was not "an unreasonable assessment".
"Our travel advice is do not travel to Ukraine," he said.
"What I'd also argue is anyone seeking to [fight with informal militias] would find themselves on the wrong end of some very, very violent attacks."
