Australia will commit $70 million in defence support - including missiles and ammunition - to Ukraine to help arm the country's outgunned military against Russia's invasion.
Prime Minister Scott Morrison announced the contribution following a meeting of the federal government's National Security Committee on Tuesday.
"We are talking missiles, ammunition, we are talking supporting them in their defence of their own homeland in Ukraine," he told reporters.
"We will do that in partnership with NATO."
The Australian government will also commit $35 million to international organisations to support their efforts to provide shelter, food and medical supplies to Ukrainians.
Ukraine's resistance to Moscow's invasion has shown resilience as residential areas have continued to face bombardment from Russian artillery.
Mr Morrison said this had seriously impacted the progress of Moscow's military offensive, but its "unlawful, violent and aggressive" intent remained.
He referenced Ukraine President Volodymyr Zelenskyy's public call for military support from allies in explaining Australia's decision to fund arms to Ukraine.
"President Zelenskyy said 'don't give me a ride, give me ammunition" and that is exactly what the Australian government has agreed to do," he said.
Mr Morrison would not elaborate on the timeline for the military equipment - funded through partners - to reach Ukraine, except to say they would get their "fast".
"I won't be giving Vladimir Putin any heads up on how it's getting there, but it's coming, I assure you," he said.
The extension of support to lethal weaponry marks a significant step up to more than $4 million already committed to non-lethal military equipment and medical supplies.
Australia continues to fast track visas
The United Nations has said more than 500,000 people have fled Ukraine to neighbouring countries since the start of Russia's invasion.
Mr Morrison said the government continued to prioritise visa applications from Ukrainian citizens and were receiving around 100 a day.
He also indicated the government were aware many Ukrainians may only want to come to Australia on a temporary basis.
"We are preparing options to support the broader humanitarian effort to have programs like we had for the Kosovar some years ago," he said.
The comments refer to temporary safe haven visas offered to Kosovars fleeing the Kosovo-Serbia conflict in the late 1990s.
As the places were designed to be temporary, they were in addition to the standard Humanitarian Program.
Mr Morrison said it was currently considering "supplementing" the existing offer of visas through this pathway in response to the crisis.
The prime minister also again addressed the prospect of Australians answering a call from Mr Zelenskyy for citizens of the world to join the fight against Ukraine.
He sharped his language on this front urging Australians to heed the advice of the Department of Foreign Affairs not to travel to the conflict zone.
"Don't do it," he said.
"The legal position at best is unclear and, as a result, we would encourage people not to join in those efforts."
Western nations have united to target Russia with sanctions, including President Vladimir Putin and his inner circle.
Mr Morrison said the maximum cost must be exacted against Russia for its actions.
"They have self-selected themselves as a pariah state," he said.
"No-one should have anything to do with them, frankly, right around the world."
