Australia is seeking advice about sanctioning Russian President Vladimir Putin and Foreign Minister Sergey Lavrov as the Kremlin pushes forward with its invasion of Ukraine.
Australian Foreign Minister Marise Payne announced the move following the United States, United Kingdom and European allies taking similar steps.
Sanctions on eight Russian oligarchs close to Mr Putin and 339 members of the Russian parliament were signed off overnight.
Key figures of the Belarusian government who have abetted Russia and the invasion will also be targeted.
Senator Payne says there is strong determination to ensure that Russia faces a high cost for its unprovoked attack.
"It is an exceptional step to sanction leaders but this is an exceptional situation," she told reporters in Sydney on Saturday.
"The next immediate priority is to continue sanctions on Vladimir Putin's inner circle and on Russia's defence industry."
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 Nation's emergency relief coordinator Martin Griffiths briefed members on the humanitarian situation overnight.
Senator Payne says 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 says 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 says more than 100 of its civilians and more than 1000 Russian troops had been killed on the invasion's second day.
An estimated 100,000 Ukrainians have fled their homes, with many trying to cross into neighbouring countries, mainly Moldova and Romania.
with Reuters