Anthony Albanese has indicated Australia would look to re-establish a diplomatic presence in Ukraine.
Ahead of talks in Spain for NATO, where the Russian invasion is high on the agenda, the prime minister said re-establishing an embassy post is a possibility.
"We would like to have a presence on the ground there to assist and to be able to provide that ground presence," he told reporters in Spain.
"I'll have more to say on that in coming days and weeks."
Ukraine's ambassador to Australia Vasyl Myroshnychenko expressed hope Australia's ambassador to Ukraine, Bruce Edwards, would be able to return to the country.
Australian embassy staff have been working out of Poland since the crisis began.
The prime minister has been invited to visit the war-torn country, but has yet to indicate if he would make the journey.
"We will continue to take security advice on that, clearly we have a security situation which is changing day by day," he said.
Australia was looking for new ways to support Ukraine in the wake of the invasion, Acting Prime Minister Richard Marles said.
"While Ukraine is a long way from Australia, we really do see that the principles which are at stake in the conflict - which is essentially that the global rules-based order that Australia stands for and helped build and protect - needs to be protected everywhere," he said.
Australia has so far promised almost $300 million worth of assistance to Ukraine, although not all had yet been handed over.
Among the military assistance was 40 Bushmaster vehicles, with 20 of them already delivered to Ukraine.
Mr Myroshnychenko said Australia had been one of Ukraine's key allies against Russian aggression.
"Australia is punching above its weight," he told Sky News on Tuesday.
"There is a tradition of Australia standing up to the bullying behaviour, and Prime Minister Albanese understands it really well.
"(The new government) haven't yet been able to announce any new assistance package but I'm sure it's in the making."
Australia has committed to providing 40 Bushmasters to Ukraine, with 20 of those having already arrived.
Ukraine's ambassador said other world leaders have made the trip, despite the danger.
"When I say nobody's safe in Ukraine, it's just the reality of the war - because it's war," he said.
"(UK Prime Minister) Boris Johnson visited Ukraine last week. We had the visit of the Italian, German and French leaders ... visitors come on a regular basis."
Should Mr Albanese go to Ukraine, it would be the first time an Australian prime minister has done so.
"Australia is very well regarded in Ukraine ... everybody is very positively surprised by how Australia has been able to stand out in this war because previously, in the past, we are so far away," Mr Myroshnychenko said.
"My president has assured me Prime Minister Albanese is very welcome, he'd be delighted to see him."
Opposition Leader Peter Dutton said he wanted to see further action from Australia.
"There's more that we can do and I'm sure that will be considered by the government," he said.
