The 31-year-old has signed a four-year deal and moves to the national set-up after a five-year spell as manager of Bristol Academy in the Women's Super League.
Sampson replaces Hope Powell who was sacked in August following a group-stage exit at the European Championships, bringing an end to her a 15-year reign.
"I'm very proud and honoured to be offered the opportunity by The FA to manage the England Women's senior team," Sampson told the FA's official website.
"Women's football in England is in a fantastic place right now, with the growth and development of the game in the last few years, and I am ready to give everything I have to build a team that every English supporter can be proud of."
England currently sit top of Group Six in their qualifying campaign for the 2015 World Cup with four wins out of four and no goals conceded under caretaker boss Brent Hills.
Powell's former assistant applied for the post and Sampson was quick to praise the man who has given him the perfect platform to build on when he takes charge for the next qualifier against Montenegro in April.
"I am also very thankful to Brent for the excellent work he has done in helping the team get off to a winning start in the qualifying campaign for the World Cup in 2015," he added.
"The aim is to build on this momentum going forwards, and I look forward to the first training camp in January.
"This is a huge challenge for me personally and one in which I'm looking forward to taking on. I hope everyone in the game can unite behind me and the squad and together we can share a new and exciting journey for women's football in England."