Scott Morrison has banned Vladimir Putin from travelling to Australia following Russia's invasion of Ukraine.
The Prime Minister took the rare step at midnight as Ukrainian troops fended off Russian forces in brutal firefights in Kyiv and other cities.
The Russian president joins only a handful of world leaders past and present to be locked out of the country, including Robert Mugabe of Zimbabwe, Muammar Gaddafi of Libya and Bashar al-Assad of Syria.
Prime Minister Scott Morrison speaks during a vigil at St Andrews Ukrainian Church in Sydney on Sunday
Russia's Foreign Minister Sergei Lavrov, Defence Minister Sergey Shoigu, Prime Minister Mikhail Mishustin, and Internal Affairs Minister Vladimir Kolokoltsev were also slapped with financial sanctions and travel bans alongside their leader.
'It is exceedingly rare to designate a head of state, and reflects the depth of our concerns,' Mr Morrison said in a statement.
The Prime Minister also said he was still finalising which weapons he will send to help Ukraine after announcing lethal support on Sunday.
'Australia will work with NATO and our other partners to provide lethal as well as non-lethal military equipment, medical supplies, and financial assistance to support the people of Ukraine,' he said.
Australia will also contribute $US3million to NATO's Trust Fund for Ukraine to buy the Ukrainians non-lethal military equipment and medical supplies.
'Details of Australia's contribution of lethal military equipment are being worked through with our partners and will be announced soon,' Mr Morrison said.
Meanwhile, NSW will divest itself of Russian assets in its investment funds, in a protest against Putin's invasion of Ukraine.
At least $75 million of Russian assets acquired by the NSW Generations Fund will be sold.
President Putin launched his invasion of Ukraine - which was part of the Soviet Union until it collapsed in 1991 - on Thursday but has still not captured any major cities due to fierce resistance.
Ukrainian soldiers take positions outside a military facility as two cars burn, in a street in Kyiv, Ukraineon Saturday
A civil defenseman stands at a checkpoint in Kyiv, Ukraine on Saturday
Last night President Putin's ally Belarus President Alexander Lukashenko issued a chilling threat that the West's sanctions on Russia are pushing the Kremlin into a Third World War, after Putin put his nuclear deterrent forces on 'alert'.
Lukashenko's comments came as Kyiv and Moscow agreed to hold peace talks at the border with Belarus - though Volodymyr Zelensky admitted he wasn't confident of a positive resolution, adding that he owed it to his people to at least try and engage.
This evening also saw the EU unveil a fresh package of sanctions against Putin's regime, closing off its airspace to all Russian planes and banning Kremlin propaganda outlets Russia Today and Sputnik.
'Now there is a lot of talk against the banking sector, gas, oil, SWIFT,' Lukashenko said. 'It's worse than war. This is pushing Russia into a Third World War. We need to be restrained here so as not to get into trouble. Because nuclear war is the end of everything.'
Zimbabwe's President Robert Mugabe (pictured in 2017) was also sanctioned. Australia imposed autonomous sanctions in relation to Zimbabwe in 2002, reflecting concerns about political violence and human rights violations
Since 2011, Australia has imposed autonomous sanctions in relation to Syria to reflect Australia's grave concern at the Syrian regime's deeply disturbing and unacceptable use of violence against its people. Pictured: Sydney President Bashar al-Assad
Australia sanctioned Libyan dictator Muammar Gaddafi (left in 2007 with former French President Nicolas Sarkozy) after the regime's use of violence against its people
Ukraine's health ministry said on Sunday that 352 civilians, including 14 children, had been killed since the beginning of Russia's invasion. It also said that 1,684 people, including 116 children, had been wounded
Ukrainian President Zelensky's office had earlier said the two delegations will meet 'without preconditions' near the Pripyat River, to the north of Chernobyl, in a deal brokered in a phone call with Lukashenko himself.
A spokesperson added that Lukashenko has taken responsibility for ensuring that all planes, helicopters and missiles stationed on Belarusian territory remain on the ground during the Ukrainian delegation's travel, talks and return.
Zelensky described his discussion with Lukashenko as 'very substantive', adding that he had made it clear he did not want troops to move from Belarus to Ukraine and Lukashenko 'assured him of this'.
He added: 'I do not really believe in the outcome of this meeting, but let them try, so that later not a single citizen of Ukraine has any doubt that I, as president, tried to stop the war.'
It came as Putin declared, in his own televised address, that he had ordered troops operating the nuclear deterrent onto a 'special regime of duty' in light of 'aggressive statements' from NATO leaders and 'unfriendly economic actions'. Nato secretary general Jens Stoltenberg responded: 'This is dangerous rhetoric'.
Ukraine filed a lawsuit against Russia at the Hague, with Mr Zelensky requesting that the UN
