Gary Neville said he is "absolutely thrilled" after being named as Valencia's new coach until the end of the season.
The La Liga outfit had been on the hunt for a new boss following Nuno Santo's departure in the wake of last weekend's defeat at Sevilla.
The former Manchester United and England defender will officially take charge at the Mestalla on Sunday, meaning his first game in charge will be a home game against French side Lyon in the Champions League.
Valencia host Barcelona on Saturday.
"I am absolutely thrilled to be given this opportunity with Valencia," Neville was quoted as saying by the BBC.
"Valencia are a huge football club of immense standing - and I know from my time as a player the passion and dedication of the Valencia fans."
Neville's brother Phil will remain on the coaching staff having taken a role as assistant manager in July.
The 40-year-old will also remain part of the England coaching set-up but he has stepped down from his duties as a pundit.
Valencia are owned by businessman Peter Lin, who also owns a stake in Salford City, the non-league club co-owned by Neville and other former United players.