The Eagles-Suns clash, confirmed in Friday's fixture release, immediately follows the previously announced season opener between traditional foes Carlton and Collingwood on Thursday, August 14.
It is the first time the AFLW season will start during the AFL home-and-away campaign, coinciding with the final two rounds of the men's competition.
Also in round one, old rivals Melbourne and the Western Bulldogs will do battle for the Hampson-Hardeman Cup and GWS host Essendon in the first-ever meeting between the sides.
Brisbane will take on North Melbourne in round five, in their first encounter since the Kangaroos' breakthrough grand-final triumph under Darren Crocker last year.
AFLW fixtures boss Josh Bowler said the league was looking to celebrate iconic moments, grow rivalries and create traditions with this season's fixture.
"It is important to recognise the moments and match-ups in the game that have helped shape the league so far, while also nurturing the emerging rivalries and making it easy and accessible for fans to attend," Bowler said.
Geelong's GMHBA Stadium is the only major AFL venue where AFLW matches will be played in 2025. None have been scheduled at premier venues in Melbourne, Sydney, Brisbane, Perth or Adelaide.
Unpopular mid-week fixtures have been dropped in 2025, except for Thursday night features in rounds one, seven and eight, with the latter two falling either side of the AFL grand final.
The fixture has been partially based on last season's ladder, divided into three groups of six, and is weighted towards ensuring more match-ups within each group.
AFLW's two major themed rounds will both be played over two weeks; Indigenous Round in rounds three and four and Pride Round across rounds nine and 10.
Intrastate rivalries are littered throughout the fixture, starting in round five when Fremantle host West Coast at the port.
Sydney and GWS clash in round six, Gold Coast take on Brisbane in round eight and Adelaide do battle with Port Adelaide in round 11.
The schedule for the final round of the home-and-away season has been left floating, to be confirmed closer to the date.
AFLW grand final hosting rights will fall to the highest-ranked preliminary final winner.
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