The funds will be placed in the 'Ukraine Energy Support Fund', run by both Ukraine and the European Commission, to be spent on whatever energy supplies Ukraine needs most.
Ukraine had made two separate requests for coal from Australia since last December, and the federal government had expressed reluctance to meet them.
That's despite coal having been provided by Australia to Ukraine early in the war.
But the government will now provide an additional $31 million in support — with $20 million for the energy fund, and $11 million in additional humanitarian support.
Foreign Minister Penny Wong said sending funds rather than coal direct was simply cheaper and easier.
"If you ship coal from Australia, you have shipping and insurance costs," she said.
"In fact this amount of money, should Ukraine wish to spend it for coal, would yield an equivalent amount of coal to what we saw previously.
"But this enables Ukraine to make its own decisions about where it best applies this funding."
Ukraine has welcomed the support, with Ambassador Vasyl Myroshnychenko saying it is much needed.
"I am deeply grateful to the Albanese government and in particular [Penny Wong] for this new package of timely assistance for Ukraine's energy security and humanitarian needs," he said.
The Coalition has also indicated its support for the additional funding, but questioned the timing of the decision.
Shadow Foreign Minister Simon Birmingham said Ukraine should not have had to wait months since its original request last year.
"Questions need to be answered by the government about why it's taken six months to respond to a request for more coal, and why money in a fund is better for Ukraine than Australian coal on a ship, as Ukraine had requested," he said.
"This is a war and Australia's responsiveness to Ukraine's requests should be swift, not drawn out and delayed."
The $11 million in humanitarian funding will go primarily towards the UN Office of Coordination for Humanitarian Affairs, focused on essentials like food, water and shelter.
Part of the funding will also go directly to supporting those with disabilities, through the UN's Partnership on the Rights of Persons with Disabilities.
