The 31-year-old becomes a non-executive director of the players' union.
PCA chief executive David Leatherdale said: "Isa has a vast knowledge of the game from a men's and women's perspective.
"With our international women players now full members of the PCA, Isa will bring real insight to the PCA board."
Guha was a Women's World Cup, World Twenty20 and Ashes winner.
After retiring in in 2012, she pursued a career in broadcasting, including for the BBC's Test Match Special.
"I am delighted to be joining the PCA at an exciting time for the game here in England for our men and women at both domestic and international levels," Guha said.
"I look forward to working with the team at the PCA, and with all the many past and present players, as the country prepares for a number of major events, starting with the ICC Champions Trophy and the Women's World Cup this summer."
Former England seamer Isa Guha has become the first woman to be appointed to the board of the Professional Cricketers' Association.