Australia will provide a further $25 million of defensive military equipment for Ukraine to help the country's military forces against Russia's invasion.
Scott Morrison announced the package - which includes tactical decoys, unmanned aerial and ground systems, rations and medical supplies - ahead of Ukrainian President Volodymyr Zelenskiy addressing parliament.
The prime minister said the assistance came at the request of the president.
"The Australian government will continue to identify opportunities for further military assistance where it is able to provide a required capability to the Ukraine Armed Forces expeditiously," he said.
The measures were announced alongside an additional 35 per cent tariff for all imports coming from Russia and Belarus on top of general duties that already apply.
The tax hike will come into effect from April 25 alongside a prohibition on Russian oil and energy products.
Australia has also granted almost 5600 visas for people in Ukraine, with more of 1400 of whom have since arrived.
Ukraine's ambassador-designate to Australia Vasyl Myroshnychenko, who arrived in Sydney on Saturday after escaping Kyiv, expects the president will repeat calls to establish a no-fly zone over Ukraine during his speech.
The ambassador said Ukraine is concerned Russian missiles could inadvertently hit one of the country's five nuclear power plants, threatening the rest of Europe.
"If we have a no-fly zone (over parts of Ukraine) this is what is going to protect the sky and this is what is going to protect the safety and security of the entire Europe," he told ABC Radio.
"Despite any news that there is any progress in the peace negotiations we are very sceptical about the true nature and true intentions of Russia."
Mr Myroshnychenko said Australia should expel the Russian ambassador to send a statement of support for Ukraine.
"Every time I watch these harrowing pictures and footage from Ukraine (of bombings) ... I believe that the Russian ambassador should be expelled," he said.
It comes as a top United Kingdom intelligence official told the National Security College in Canberra that the Russian president has misjudged the resistance of the Ukrainian people, with Russian soldiers losing morale and refusing to follow orders.
"(Vladimir Putin) over-estimated the abilities of his military to secure a rapid victory," Sir Jeremy Fleming said.
"We've seen Russian soldiers - short of weapons and morale - refusing to carry out orders, sabotaging their own equipment and even accidentally shooting down their own aircraft."
Sir Jeremy, who heads the Government Communications Headquarters, also said Russia had turned to China for weapons, technology and as a means to circumvent sanctions.
But risks remain for the alliance into the future, he said.
"Russia understands that long term, China will become increasingly strong militarily and economically. If some of their interests conflict; Russia could be squeezed out of the equation.
"And it is equally clear that a China that wants to set the rules of the road - the norms for a new global governance - is not well served by close alliance with a regime that wilfully and illegally ignores them all."
Australia is providing $91 million in military assistance, $65 million in humanitarian assistance and 70,000 tonnes of thermal coal to meet Ukraine's energy needs, as well as temporary protection visas and support for Ukrainian community groups in Australia.
There are also targeted sanctions on individuals and entities, the prohibition of energy, oil and gas products from Russia, and a ban on exports of alumina and bauxite to Russia.
with Reuters
