Home Affairs Minister Tony Burke said the group, made up of four women and nine children, have finalised plans to come back to Australia after spending years stranded in a Syrian refugee camp.
Mr Burke said the government was not assisting the group in any way.
"These are people who have made the horrific choice to join a dangerous terrorist organisation and to place their children in an unspeakable situation," he said.
"Any members of this cohort who have committed crimes can expect to face the full force of the law."
Mr Burke said officials were alerted about the group's return when they left the refugee camp.
He said there were limits on how citizens could be blocked from returning to Australia.
"I have received advice in one instance so far of (a temporary exclusion) threshold having been met, and when I received that advice, I acted immediately at that exclusion order," he said.
Australian Federal Police Commissioner Krissy Barrett said members of the group faced the prospect of being arrested on their return, but did not say how many.
"Some individuals will be arrested and charged. Some will face continued investigations when they arrive in Australia," she told reporters in Canberra.
"Children who return in the cohort will be asked to undergo community integration programs, therapeutic support, and countering violent extremist programs."
It was revealed in late April that the group of 13 had left the al-Roj camp to travel to the Syrian capital Damascus with plans to board a flight back to Australia.
They were yet to depart at that point and it was unclear if they had secured plane tickets to return.
Mr Burke said Australian intelligence agencies had been preparing for a potential return of the group since 2014 and plans are in place to monitor them.
"The priority of the government, as always, is the safety of the Australian community," he said.
A group of about 30 women and children has been trying to return home to Australia from Syria for years after travelling to the Middle East with men who sought to fight for Islamic State before the caliphate was toppled in 2019.
The larger cohort recently attempted to leave the al-Roj camp for Damascus in order to travel to Australia but were turned around by local authorities and forced to return.
Opposition home affairs spokesman Jonathon Duniam said the government needed to revoke travel documents.
"It is not in the national interest. Where are these people going to be settled? What monitoring arrangements are going to be put in place? How much is it going to cost Australian taxpayers?" he told reporters in Hobart
"These are women who chose to go to Syria, to a designated terror hot spot declared under law as a crime. That is something that should not be taken lightly."
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