The group will arrive in Sydney and Melbourne on Thursday after years in a Syrian refugee camp.
Some of the women, who travelled to the Middle East with their partners who wanted to fight for ISIS, will be arrested on arrival, federal police say.
But the children face an uncertain future, with many having grown up in squalid conditions where violence and radical ideologies are commonplace.
Four women and nine children have booked tickets from Damascus to Australia, the government confirmed on Wednesday.
They are the latest group of so-called "ISIS brides" to return after the collapse of the Islamic caliphate in 2019.
While some women travelled willingly to support their partners who wanted to fight for Islamic State, advocates for the group say others were trafficked, or only went to the Middle East to keep their family together.
All children in the group of 13 returning home would likely need help integrating into Australian society after years in Syrian camps, while others could need more intensive deradicalisation support, leading extremism researcher Michele Grossman told AAP.
"This is going to be very much case by case," the Deakin University professor said.
"We can't make assumptions that all children will respond equally ... to the kinds of indoctrination activities that we know have gone on in those camps."
Prof Grossman said support from the community would be crucial to help them recover from years of trauma.
"Communities have to be willing - with appropriate support, with appropriate knowledge and transparency - to be part of the picture," she said.
"If the community is only ever going to turn them away and refuse to have anything to do with them ... then what hope are you giving them, and what prospects are you offering them?"
One woman has been barred from entering Australia on national security grounds and the opposition has reiterated its calls for the entire cohort to be blocked.
"These are people that went to support a terrorist organisation, not on holiday and got caught on some misdemeanour," opposition home affairs spokesman Jonno Duniam told reporters in Hobart.
"Serious crimes, serious risks to our community."
But Home Affairs Minister Tony Burke said there were limits on the government's ability to prevent citizens returning to their home country.
While each child would be different, many of them would have little memory of what Australia was like, violent extremism specialist Peta Lowe told AAP.
Previously director of countering violent extremism in NSW Youth Justice, Ms Lowe said some of the children might have more complex needs but others could only need a safe environment to reintegrate.
"It may not be any conversations at all about religion or political beliefs," she said.
"It may be around those very normal things that we would do for children when they've come out of risky situations."
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