The ex defender has signed a deal with England that will lat for four years and will allow him to continue his work at Sky Sports.
The new job starts straight away and Neville will be putting the squad through their paces next week as they prepare for Euro 2012.
Neville was capped for England 85 times and has been called the best right-back of his generation.
There is no doubt that Neville is pleased with his new role, He said: “Roy asking me to be a part of his staff and to work with the national team is not only an honour but a very special moment for me.
“I had absolutely no hesitation in accepting this role and I am relishing the opportunity to work alongside Roy and the team at the Euros and through to the next two tournaments.”