Operation Kudu will be extended by a year and the number of Australian troops sent over each rotation will increase to 90.
Focus areas include urban and trench warfare, combat first aid, explosive hazard awareness and shooting.
More than 30,000 Ukrainians have been trained since June 2022.
Defence Minister Richard Marles will officially announce the expansion in Darwin on Thursday as he welcomes back troops from the last rotation.
"We are proud to expand Australia's support for Operation Kudu, a mission that cements international solidarity for Ukraine," he said.
"Our growing commitment to the multinational training mission affirms our pledge to provide meaningful and relevant support to the government and people of Ukraine."
Training Ukrainian soldiers was an important way for Australia to help Kyiv end the war on its own terms, Foreign Minister Penny Wong said.
"Australia is proud to stand shoulder to shoulder with the brave Ukrainians who are defending their people, their territory, and their sovereignty," she said.
Australia has provided about $910 million in aid to Ukraine, including $730 million in military assistance.
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