Ukraine has welcomed Australia's donation of an extra 30 Bushmasters to its war effort against Russia.
Canberra is also sending up to 70 defence force trainers to the United Kingdom in its latest effort to prop up Kyiv.
The personnel will be deployed to the UK in January to join a British-led operation to train Ukrainian troops.
No Australian defence personnel will enter Ukraine.
Australian troops joining Operation INTERFLEX will help prepare their Ukrainian counterparts to continue the fight.
Ukraine's ambassador Vasyl Myroshnychenko welcomed the aid, saying the Bushmasters have "helped us liberate swathes of land".
"On the training side, it's great news," he told AAP.
"That will contribute to creating personal connections and serve as a good foundation, on a human-to-human level, to advance our bonds in the future."
Defence Minister Richard Marles said training the underskilled Ukrainian troops was vital.
"What we're seeing in Ukraine now is really a reservist force, so that's everyday Ukrainians signing up to be servicemen and women in the defence forces," he told the Nine Network.
No timeframe has been given for how long troops will remain in the UK.
Troops who will be best placed to deliver the training will be selected to go.
"There'll be a process about looking at who is in the best position to provide that training and where those people sit within our own preparedness roster," he told Sky News.
"The way in which we prepare or choose people for deployments is a well-honed process now."
Mr Marles said supporting Ukraine was in Australia's national interest because repercussions would have a global effect.
He said support would continue to flow for "as long as it takes", warning of a protracted conflict.
"We need to have support there for Ukraine over the long term," he said.
"This next tranche of support reflects that."
The new measures bring the value of Australia's total support for Ukraine to $655 million, including $475 million in military aid.
Australia has donated 90 armoured vehicles.
The additional costs will come from the defence department, after Tuesday's federal budget revealed the government will provide more than $210 million to Ukraine over five years.
