Valencia presented Dutchman Ronald Koeman as their new coach on Friday.
Valencia president Juan Soler described former the Netherlands and FC Barcelona player as a coach of "international renown," who he hoped would make two-time Champions League runners-up Valencia "one of the best clubs in Europe."
Koeman, who quit PSV Eindhoven on Wednesday to replace the fired Quique Sanchez Flores, has joined on a contract until June 2010.
"Koeman is a soccer man, someone who was singled out by the club's management," Soler was quoted as saying by Valencia's Web site. "We are convinced we will be in good hands."
Valencia has agreed to compensate PSV with an undisclosed sum for the loss of Koeman, who was under contract until next year, and his assistant coach Tonny Bruins Slot.
Koeman arrives with Valencia having lost five of their past six games. Two days after Sanchez Flores' departure on Monday, the team crashed 5-1 to Real Madrid for their worst home defeat for 74 years.
Valencia have dropped to sixth place in the league with 18 points from 10 games, seven fewer than leaders Real Madrid. They are third in Champions League Group B, having lost two of their first three games.
Koeman won't take charge of the team until tomorrow, a day before the Champions League match against Rosenborg at the Mestalla Stadium.
Koeman enjoyed great success in Spain as a defender during the 1990s with Barcelona, scoring to make Barcelona European Champions for the first time in 1992.
He was also a European champion with PSV and helped the Netherlands win the 1988 European Championship.
Koeman's first coaching experience came as an assistant at Barcelona before his appointment by Vitesse Arnhem in 2000. He then took charge of Ajax and won two Dutch leagues before moving on to Benfica.
His most recent success came last season when he guided PSV to their 20th league title.