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The 33-year-old made the announcement in a heartfelt message on Twitter.
White said: "This decision has always been one I have wanted to make on my terms. And this is my time to say goodbye to football and watch the next generation shine."
White played a key role as the Lionesses clinched the European Championships this summer, starting every match and scoring twice to take her final record for her country to 52 goals with 113 caps.
She represented England at three Euros and three World Cups, scoring six goals at the 2019 tournament.
England Women's head coach Sarina Wiegman said: "Ellen has given so much for England and we are all so proud of her. I have only had the pleasure of working with her for this past year, but her professionalism, work rate and finishing ability is world-class.
"This summer, she did an amazing job for the team, she is the perfect team player and helped the younger players to find their way in international football. I already knew she was a great player but I found an even better person. We will miss her, but I fully understand her decision to take a new direction."
At domestic level, White won both the WSL and FA Cup twice with Arsenal before lifting the FA Cup again with Manchester City in 2020. She signed a two-year contract with City the following year, but will not see out her current deal.
Baroness Sue Campbell, The FA's director of women's football, said: "Ellen White will long be remembered as a model for others to follow. It is not just about her record-breaking 52 goals and performances on the pitch, but about the standards she set and the way she conducts herself.
"A true leader of women, it has never been about Ellen White for her - even when she was scoring the crucial goals or giving everything she had, it was always the team first. She is a legend of the modern game."
The FA plans to recognise White's career at one of England's home autumn fixtures.
'White walks away as one of England's all-time best players'
Sky Sports News reporter Anton Toloui:
"I think the news has caught a lot of people by surprise. It seemed a little bit odd that White didn't take part in the two Champions League qualifiers the past week for Manchester City and she didn't return to pre-season training.
"You smelt a rat last week when Gareth Taylor, the head coach for City mentioned giving her some time off for personal reasons. It felt like something was bubbling, but you didn't expect it to be a full-blown retirement.
"White walks away as one of England's all-time best players, one short of Wayne Rooney's 53 goals for the country. In her statement, she talks about the hard work and graft.
"That is what she sees in herself - she won the WSL early on in her career twice with Arsenal but she then suffered two ACL injuries, came back stronger and peaked later.
"Ask anyone she's played with and they'll tell you she was one of the best finishers they've ever played with. She's been a huge part of English football for over a decade.
"She was a big-game player who will be remembered predominantly for her goals. She was arguably England's best player at the last World Cup and it's her work ethic that stood out.
"She's someone who has unified teams, putting her arm around young players as she did at the Euros. She didn't have her best tournament this summer, but she is a player's player. That is the legacy she will leave."
Watch the Women's Super League with Sky
The 2022/23 Women's Super League season kicks off on the weekend of September 10/11, with defending champions Chelsea starting at home to West Ham.
That curtain-raising round of fixtures also features a match-up between the teams which finished second and third in the WSL last season, with Arsenal going to Manchester City.
Arsenal only missed out on the title by a point last season, so their home match with Chelsea on the weekend of January 14/15 - the first round of games after the WSL's month-long winter break - and trip to face Emma Hayes' side on the penultimate weekend of the season, May 20/21, could be pivotal.