Neville, who also played for England and Everton and was previously first-team coach at Manchester United and assistant coach at Spanish club Valencia, takes over from Mo Marley, who was put in charge of the team on an interim basis following Sampson's exit.
"I am honoured to be given the chance to lead England," the 41-year-old Neville, whose sister Tracey is head coach of England's netball team, said in a statement on the FA website.
"With the new coaching team we are putting in place, we can help the players build on their great progress in recent years. This squad is on the verge of something special and I believe I can lead them to the next level."
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England are currently ranked third in the world and will be expected to mount a strong challenge at the 2019 World Cup in France.
Neville's appointment comes a week after his former Manchester United team mate and fellow "Class of 92" member Ryan Giggs was named Wales manager.
Sue Campbell, the FA director of women's football who oversaw the recruitment process, paid tribute to Marley, who will return to her role leading England's development squads, and welcomed Neville's appointment on a three-year contract.
"His enthusiasm, passion and desire for the role impressed us all and once he emerged as a candidate, we knew we had the right person for this talented squad," she said.
"With the other coaches we'll appoint, working closely with Phil and complementing his coaching prowess and international experience, we have an exciting team that will help the squad make yet another jump forward."
(Reporting by Simon Jennings in Bengaluru; Editing by Toby Davis)
