Foreign Affairs Marise Payne says Australia is taking steps to impose sanctions on Russia's President Vladimir Putin and Foreign Minister Sergey Lavrov.
The United States, the United Kingdom, the European Union and Canada made the announcement to punish Mr Putin overnight, and Australia is looking to follow suit.
"It is an exceptional step to sanction leaders but this is an exceptional situation," Senator Payne told reporters on Saturday morning.
"There is very strong agreement and determination to ensure that Russia faces a high cost for what is a completely unprovoked and unjustified attack on its neighbour."
Australia has announced a further round of sanctions, sanctioning eight Russian oligarchs and 339 members of the Russian parliament who Ms Payne said are "political facilitators" of the invasion.
Senator Payne said key figures in the Belarusian government have also been targeted "who are abetting the invasion".
"The invasion is a wholesale breach of international law. It is a breach of the UN charter and the most flagrant violation of sovereignty and territorial integrity that Europe has seen in decades," she said.
The foreign minister says the blame lay squarely at the feet of the Russian president.
"We need to be absolutely clear - Vladimir Putin has unparalleled personal power over his country and he has chosen to go to war against a neighbour that posed no threat to Russia," she said.
"It is clear that the only way to exact a cost for those actions is to ensure that he, himself, shares some of that cost and some of the pain that he is inflicting on everyone else around him in Ukraine."
Australia will provide non-lethal military and medical aid to Ukraine through NATO and support will be guided by requests from Kyiv.
It will also continue to provide cyber security assistance.
The United Nations' emergency relief coordinator Martin Griffiths briefed members on the humanitarian situation overnight.
Senator Payne said the full scale of tragedy and death toll remains unclear due to the difficult security situation.
"We will be ready to provide humanitarian assistance as the situation in Ukraine and in surrounding countries becomes clearer," she said.
The expelling of Russian diplomats from Australia remains an option but Senator Payne said it is not something currently being considered by the government.
"It enables us to have a direct line of communication with the Russian government," the foreign minister said.
There remain no direct or specific cyber threats against Australian businesses.
Ukraine said more than 100 of its civilians and more than 1,000 Russian troops had been killed on the invasion's second day.
, with many trying to cross into neighbouring countries, mainly Moldova and Romania.
