BBC Sport reported on Tuesday the former England international had been given a contract until 2021, taking over from interim boss Mo Marley.
Neville expressed his delight at the appointment after coaching roles with United and Valencia, and a spell working for the FA with the England under-21 squad.
"This squad's on the verge of something special and I believe I can lead them to the next level.
"I am honoured to be given the chance to lead England. With the new coaching team we are putting in place, we can help the players build on their great progress in recent years.
"There is no greater honour than representing your country and it will be a privilege to do it again."
Neville learned his trade under the guidance of legendary United manager Sir Alex Ferguson, playing for the Red Devils for 11 years until 2005.
He won six Premier League titles, three FA Cups and one UEFA Champions League at Old Trafford before joining Everton.
The 41-year-old has had a successful career as a media pundit, but this will be his first major managerial role.