Ex-Matilda Kate Gill will share the role of PFA chief executive with former A-League player Beau Busch.
The pair are taking over from John Didulica, who stepped down from the position as boss of Australia's football players' union at the start of the month.
Gill's elevation to the role continues her groundbreaking path through the PFA's executive.
After becoming the first female player to be elected to the PFA executive in 2014, Gill had most recently been working as Didulica's deputy CEO.
"The PFA has always been about the players and there is nothing more rewarding than knowing that your peers and former teammates have confidence in you to lead their organisation," Gill said.
Busch, a former Sydney FC and North Queensland Fury player, steps into the shared role after being the PFA's head of player relations.
"Both have a significant history of contribution to the PFA including during their playing careers," PFA president and Sydney FC captain Alex Wilkinson said.
"Their joint appointment recognises their commitment to working together as a team to serve the players and the game at what is a very challenging time with critical industrial, commercial and structural negotiations all due."
Australian Associated Press