The 64-year-old has signed a one-year deal and he will take up the post with PSV after Euro 2012.
“PSV wanted to attract an elite coach in Dick Advocaat and he was enthusiastic about joining PSV,” the club’s technical director, Marcel Brands, told their official website.
“His decision to join PSV, despite very lucrative financial offers from Russia, strengthens our confidence in this cooperation.
“He knows the club from a previous spell here and sees great potential in the squad of players.
“Advocaat is also looking forward to working with a number of young assistants, who also had a successful past as a player under him at PSV.”