Vladimir Teslov, a 27-year-old man from Victoria, was arrested in Brisbane's southwest on Thursday and charged with attempting to engage in foreign interference.
Teslov reportedly travelled to Russia in October 2024 for military-style training, before returning to Australia and going to Ukraine the following year to join the Ukrainian armed forces.
He then allegedly provided the location and operation of Ukrainian military activities to Russian forces as part of the country's ongoing war.
The man maintained contact with individuals he believed were connected to Russian intelligence services, AFP Commissioner Krissy Barrett told reporters in Canberra.
"Investigators will allege the man then travelled to Ukraine in May 2025, where he joined the Ukrainian armed forces, gaining access to information relating to military personnel, units and locations," she said.
Ms Barrett stressed there was no threat to Australia as a result of the man's alleged offending.
"There is nothing to suggest he received any military training in Australia and, in terms of the training he undertook in Russia, that is part of our ongoing investigations," she said.
Asked whether the man would have been charged if he was accused of supplying Russian information to Ukraine's troops, Ms Barrett said it was the job of the AFP to target criminal offending rather than specific countries.
"Our job is ensuring that Australia does not become a safe haven for people who think they can conduct foreign interference on our shores. This is about sending a message," she said.
She declined to say whether police had begun the investigation on the advice of Ukraine.
Teslov's arrest came following an investigation by the AFP's counter foreign interference task force.
It's the first time the task force has charged a Russian-linked person under foreign interference laws, following a change in priorities when Ms Barrett took up her role.
"Foreign interference is an insidious crime, and it has a bigger impact on Australia than what many people realise," she said.
"Offenders who engage in these crimes can leave our nation vulnerable to security threats."
Ms Barrett said police carried out search warrants at two properties in Brisbane on Thursday, and acted in relation to further warrants on Friday.
Teslov did not appear or apply for bail when his case was mentioned in a Brisbane magistrate's court on Friday, represented by LegalAid.