Foreign Minister Penny Wong says she is deeply concerned by reports Russian missiles have strayed into Poland.
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Two people have been killed in an explosion in eastern Poland, 12km from the Ukrainian border, with US and western allies investigating the incident.
Russia's defence ministry has denied the explosion came from a stray missile.
The incident could threaten an escalation of the war in Ukraine, with Poland being a NATO member.
Members of NATO countries are committed to collective defence as part of the alliance.
Australia stands alongside Ukraine in condemning the attacks, Senator Wong said.
"Reports these missiles have also struck Polish territory are deeply concerning," she said in a statement on Wednesday.
"We again call on Russia to withdraw its forces and end its illegal, immoral war."
US President Joe Biden has held talks with Polish President Andrzej Duda since the incident.
Ukraine's ambassador to Australia Vasyl Myroshnychenko said Ukraine was expecting a response from NATO.
"It will be up to NATO to decide how to react to this," he told the Seven Network.
"As we can see, Russia is a terrorist state. It is unacceptable what they are doing and how they are making life unbearable for the civilians."
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Opposition Leader Peter Dutton said he was troubled by the latest developments in the conflict.
"There are neighbouring countries who have been very worried, Poland in particular, because of the threat not just of conventional war but the prospect of nuclear war under President (Vladimir) Putin," he told Sky News.
"To see people killed in Poland now is a tragedy for them and for their families, for the country, but for the region as well."
Australian Associated Press
