Valencia has announced that the 38-year-old has been appointed to coach Nuno Espirito Santo's backroom team at Los Che, which finished fourth in the Primera Division last season.
Neville has experience of coaching at Manchester United, where he worked with current Real Sociedad boss David Moyes, and England Under-21's.
A statement on www.valenciacf.com read: "Valencia CF are pleased to announce the appointment of Phil Neville as assistant manager of the first team, joining the coaching staff headed by Nuno Espirito Santo.
"The former Manchester United and Everton player has previously occupied the assistant role at Old Trafford, under both David Moyes and interim replacement Ryan Giggs. Neville offers a wealth of footballing knowledge to a club in constant growth."
Neville won 59 caps for England and lifted the UEFA Champions League, six Premier League titles and three FA Cups during his time with United.
He finished a 19-year playing career at Everton in 2013 before turning his focus to coaching.
The 41-year-old Nuno, who took charge of Valencia last northern summer, said: "Phil Neville has great experience at the top level of competition, but above all he has knowledge and values that fit perfectly with our team and our club.
"He has always been a team player, and our philosophy is based on teamwork. We are - and want to continue to be - a group. I am convinced that he is going to help us a lot."
Valencia regularly finishes in the top four of La Liga but last won the title in 2004 and has not won any major silverware since claiming the Copa del Rey in 2008.
