Thirty-four people attempted to leave the Al Roj refugee camp on Monday local time, but returned shortly after because of an administrative issue, a Syrian official told Reuters.
Anthony Albanese said if the group were able to travel to the capital Damascus and board a flight to Australia - as originally planned - they would likely face criminal charges on their return.
"My mother would have said, 'If you make your bed, you lie in it'," he told ABC TV on Tuesday.
"If there are any breaches of the law, they will face the full force of the Australian law if they come back."
The group of Australian citizens is believed to be made up of the partners and children of former Islamic State fighters, who travelled to the Middle East to fight for the caliphate before it was toppled by US forces.
Since 2019, the women and children have been living in Syrian refugee camps and prisons.
Some of the women - known informally as ISIS brides - have claimed they were coerced into leaving Australia.
Mr Albanese agreed the situation was unfortunate for the children involved, but insisted the government would not help the group return to Australia.
"These are people who went overseas supporting Islamic State and went there to provide support for people who basically want a caliphate," he said.
Government officials have long said they cannot stop Australian citizens from returning home of their own accord, and are obliged to provide them with passports if they can get to an Australian consulate or embassy.
Opposition senator Sarah Henderson said there were still unanswered questions about the government's involvement in the group's potential return.
"If these are people who subscribed to ISIS ideology, who subscribe to this extremist ideology, then they should not be returning to Australia," she told ABC radio.
