The announcement of the trans-Tasman Test provides the first details of the international calendar which is expected to include an Oceania series and Great Britain Lions tour to New Zealand and Papua New Guinea.
It will be the first time the Kangaroos have hosted the Kiwis in Australia since the mid-season ANZAC Test was cancelled in 2017.
The two nations have only met once since, with New Zealand defeating Australia in Auckland last October.
The double-header will feature a women's Test between the Jillaroos and Kiwi Ferns, who previously played in Wollongong in 2014.
It will also be the first time the Australian Kangaroos take on the New Zealand Kiwis at WIN Stadium.
NRL CEO Todd Greenberg said having international rugby league back in the Illawarra was a great result for region and the game.
"Rugby league has a home in the Illawarra, so we're delighted to bring the pinnacle of rugby league back to Wollongong for the first time in five years," Greenberg said.
"We recorded one of the best-ever attendances for WIN Stadium the last time Test match rugby league was played in Wollongong.
"So, I've got no doubt the local support will be strong and compliment those travelling fans who can't wait to be at the Stadium come October 25th.
"I'd especially like to thank the New South Wales Government and Destination NSW for their support of such an important event on the rugby league calendar."
The women's and men's matches will be broadcast live nationally across the Nine Network, Fox Sports and NRL Live Pass, as well as Sky NZ in New Zealand.
The Trans-Tasman Double Header is supported by the New South Wales Government and Destination New South Wales.