The former Espanyol and Deportivo La Coruna midfielder has coached with Espanyol B since retiring in 2011 and will succeed Javier Aguirre at Estadi Cornella-El Prat.
Aguirre, who took over midway through the 2012-13 campaign, left the club after leading them to a 14th-placed finish last term.
Espanyol endured a dismal end to last season, winning just one of their final 11 games, and Gonzalez - who spent three campaigns with the club as a player - will be expected to improve on Aguirre's performance next term.
Sporting director Oscar Perarnau said: "We love the personality (Gonzalez has) and the proposed game he wants to play.
"We believe fully in (his) ability."
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