The former Manchester United, Everton and England player become the permanent successor to Mark Sampson, who was sacked last September, on Tuesday.
But a historical tweet from 2012 marred the announcement with Neville then appearing to remove the sexist post with the account, fizzer18, now appearing unavailable to users of the social media site.
"Morning men couple of hours cricket be4 work sets me up nicely for the day," Neville wrote in a post six years ago.
When asked why he only referred to men, Neville replied: "When I said morning men I thought the women would of been busy preparing breakfast/getting kids ready/making the beds-sorry morning women!"
A further tweet from the account read: “Relax I’m back chilled – just battered the wife!!! Feel better now!” Another from December 2012, reads: “U women of [sic] always wanted equality until it comes to paying the bills #hypocrites”
Neville released a statement on Wednesday to clarify that the views expressed in the posts weren't "a true and genuine reflection" of his character.
“Following comments made a number of years ago I would like to clarify that they were not and are not a true and genuine reflection of either my character or beliefs, and would like to apologise," he said. “I am fully aware of my responsibilities as the England Women’s head coach and am immensely proud and honoured to have been given the role.
"I am now looking forward to the future and will work tirelessly to try and help bring success to the team.”
This controversy is the latest in a long line surrounding the Lionesses following the sacking of Sampson late last year.
Sampson was accused of racism by England striker Eni Aluko, although he was eventually sacked for "inappropriate and unacceptable behaviour" in a previous role with Bristol Academy.
That prompted the FA to turn to England U19 coach Mo Marley as a caretaker manager and she led England to a 1-0 defeat by France in a friendly in October and two convincing World Cup qualifying wins over Bosnia and Herzegovina and Kazakhstan.
Neville takes over a team that is third in the world rankings, behind only the United States and Germany and the 41-year-old is delighted to be given such an opportunity, a first of his managerial career.
"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," Neville said. "This squad is on the verge of something special and I believe I can lead them to the next level.
"I can't wait to get out on the training pitch and down to work with an elite group of players at the top of their game. There is no greater honour than representing your country and it will be a privilege to do it again."
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