The 41-year-old becomes the permanent successor to Mark Sampson and inherits a squad that will be one of the favourites to lift the 2019 World Cup.
"With the new coaching team we are putting in place, we can help the players build on their great progress in recent years," he said after his appointment was confirmed on a contract that runs until 2021.
"There is no greater honour than representing your country and it will be a privilege to do it again."
Neville will start his tenure with three prestige friendlies at the She Believes Cup.
Fast becoming a key part of the calendar for the Lionesses due to the quality of the opposition involved, England will once again take on Germany, hosts USA and France.
The matches will take place at the beginning of March in Columbus, New Jersey and Orlando City and will serve as both a further yardstick of England's progress and also a warm-up for a year of World Cup qualifying matches.
England's qualifying group is shaping up to be a battle between themselves and Wales, the Welsh currently a point clear at the top of the group but with one game more played than the Lionesses.
Southampton's St Mary's Stadium will host the home fixture between the two sides on Friday 6 April 2018 and a special early-bird ticket offer is in place until 31 January.
Adult tickets purchased before then will cost £7.50 (£10 afterwards). Children and concession tickets are just £1.
Full details at the FA website.