The former Manchester United and Everton midfielder played 59 times for England and has won 10 major trophies, including six Premier League titles.
But his first taste of women’s football will involve taking on the top two teams in the world – United States and Germany – plus France, in the She Believes Cup, starting on 1 March.
Predecessor Sampson was sacked from his position following evidence of “inappropriate and unacceptable behaviour” in a previous role.
Under Sampson, England reached the Euro 2017 semi-finals, losing to eventual winners the Netherlands, having come third at the 2015 World Cup – their best finish at the tournament.
Former England women goalkeeper Rachel Brown-Finnis would have preferred to see a woman appointed as his successor, but believes there were no suitable candidates.
“I think they shouldn’t hire someone just because they’re female,” she told BBC Radio 5 live.
“Phil Neville doesn’t have that senior level management experience but what he does bring is pretty unique.
“He trained and played as a top-level player in an era when Manchester United won everything. He has that level of excellence that the players will thrive on.”