Neville will link up with brother Phil who was appointed a coach at Valencia in July. He worked under Nuno Espirito Santo, who resigned after Sunday's 1-0 defeat at Sevilla.
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Neville had a long and illustrious playing career at Manchester United. He won 17 major honors in his 20 years at the club after making his debut for the senior side in 1992.
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He played his entire Old Trafford career under one manager -- Alex Ferguson. The Scot, widely regarded as one of the greatest coaches of all time, helped Neville win eight English Premier League titles and two European Champions League crowns during his time at the club.
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He was known for his committed style and his often controversial comments about United's great rivals Liverpool. In this 2010 match, he clashed with Jamie Carragher, who he would later work with as a pundit.
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Neville is a close friend of David Beckham, and the two formed a profitable partnership down United's right flank for a number of years before the latter left for Spanish giants Real Madrid in 2003.
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The defender represented his country 85 times after making his debut for the national side in 1995. He featured in three European Championships and two World Cups for his country.
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Neville won his second Champions League title in 2008 when a Cristiano Ronaldo inspired United beat Chelsea on penalties in Moscow.
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After retiring in 2011, Neville accepted a job as part of England coach Roy Hodgson's staff. He will combine his role as Valencia coach with his involvement with the national side, who are preparing for next year's European Championships.
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Neville has also carved out a reputation as a respected soccer pundit, writing a regular column for The Times newspaper, as well as appearing on television for Sky Sports.
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He is also a co-owner of non-league club Salford Town along with former Man Utd colleagues Nicky Butt (pictured), Ryan Giggs, Paul Scholes and brother Phil. Salford is half owned by Singaporean businessman Peter Lim, who also owns Valencia.
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Neville also has commercial business interests and owns a hotel near Manchester United's Old Trafford ground, as well as Cafe Football restaurants in Manchester and London with Giggs.