Arnell, who retired after playing in the Brisbane Lions' 2021 AFLW premiership, joins Bec Goddard (Hawthorn) and Natalie Wood (Essendon) as another female head coach in next season's competition.
The announcement of Arnell's appointment comes as speculation swirls around the future of Adelaide superstar Erin Phillips and if she will make the switch to Port, the club her father Greg starred for in the SANFL.
Arnell will bring a wealth of experience to the coaching role after being a foundation player with Carlton, before a successful stint with the Lions.
The 35-year-old was a three-time All-Australian with the Darebin Falcons before the AFLW launched in 2017.
Arnell spent a decade working as a teacher and has held AFL and AFLW media roles in recent years.
"The history of success at Port Adelaide and the expectations that come with this are not lost on me," she said.
"I want be part of something great and I can already see we are building something special within our AFLW program.
"Our female athletes will enjoy world class training facilities and will provide future generations of young girls and women a pathway to represent Port Adelaide on the national stage.
"To be the first AFLW coach in a club that is more than 150 years old is truly humbling and I can't wait for our team to write their own chapter in Port Adelaide's rich history of success."
After the Crows won Saturday's grand final for their third premiership, the next AFLW season is expected to begin in August as the league makes the shift away from summer.
Port, Hawthorn, Essendon and the Sydney Swans will play in the next AFLW season to ensure all clubs are represented in the women's competition for the first time.
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