The Tottenham Hotspur boss was quick to congratulate the former Manchester United man.
The former Manchester United right-back has been a pundit and a coach of the England national side since hanging up his boots but now he will try his hand at management in La Liga, one of the toughest arenas in world football.
Neville certainly has the intelligence and the experience to succeed but only time will tell if he has made the right move.
Speaking to ESPN after the appointment, the Tottenham boss said, “I sent a text to him to wish him all the best because he is my colleague.
“He is a brilliant man and I wish him all the best. It’s a difficult job to take Valencia now.”
The Spanish side are currently ninth in La Liga with 19 points from their first 13 matches but they have won just four of their last 10 league games and Neville will be tasked with leading them up the table as soon as possible.
Pochettino knows all too well how it feels taking charge of a club in an unfamiliar country having arrived at Southampton prior to his switch to Tottenham, and Neville will surely appreciate all the support that comes his way following his huge decision.