It is Redfearn's third appointment in women's football, having previously managed Doncaster Rovers Belles and Liverpool Ladies, with the latter being a brief spell in the summer of 2018.
During his time with Doncaster, the Belles won the FA WSL 2 title in May 2018, their first trophy since 1994.
Redfearn, a legend in his playing days at Barnsley with Doncaster Rovers and Bradford City also among his other clubs, latterly worked as under-23 coach at Newcastle United, his last role in the game.
The 55-year-old enjoyed a successful spell at Leeds academy, having to bring through the likes of Sam Byram, Lewis Cook, Alex Mowatt and Kalvin Phillips and was head coach for most of the 2014-15 season.
He has also previously served as caretaker boss for three brief separate spells.
Redfearn replaces Carla Ward, who has since joined Birmingham.
On being appointed, Redfearn said: "It's very exciting. It's a massive club and the women's team has made good strides over the past couple of seasons, so it's a good place to be."
Last month, former Barnsley head coach Paul Heckingbottom joined the Blades men's team as their lead U23 coach.