Marcelino has won the Copa del Rey with Valencia and lost two finals while in charge at Athletic Bilbao
Manager Marcelino will leave Villarreal at the end of the season.
The 60-year-old has secured Champions League football for a second straight year with Villarreal currently in third place in La Liga.
Confirming his imminent departure, the Spanish club said: "Thank you from the bottom of our hearts, Marce, for everything you have given to this club and its fans.
"We wish you all the best in your future sporting endeavours."
