The announcement comes just 24 hours after the Lionesses' all-time record goalscorer Ellen White revealed her decision to hang up her boots at the age of 33.
Born in Sunderland, Scott's remarkable 16-year career began with the Black Cats academy before representing Everton, Manchester City and Aston Villa at senior level.
After spending seven years at Everton, Scott enjoyed the majority of her success during a trophy-laden eight-year stint at Man City, winning every domestic honour including a Women's Super League title, three FA Cups and three Continental League Cups.
The midfielder made her Lionesses debut back in 2006 and went on to score 27 goals in 161 international appearances, becoming the second-most capped England player across the Men's and Women's game behind Fara Williams (172).
Scott has played at 10 major international tournaments, including eight with the Lionesses and two with Great Britain at the Olympics, and she is the only player in history to have played for England in two major international finals.
Scott wrote a lengthy statement, via the Players Tribune, on her retirement, sharing fond memories of her life and career in the beautiful game.
"I may be saying my goodbyes to football, but we're going to make this a celebration. No sad faces!! We've had too much fun for any tears," she said in her statement.
"Maybe it's because I'm from Sunderland, but two things have always been true about me: I've always been stubborn and I've always loved football. It's been in my blood ever since I was five years old.
Scott added: "Imagine, if you would have told me then that I'd go on to play for England for 16 years? If you would have told me that I'd live to see 90,000 people packed into Wembley Stadium for a women's European final? And that I'd be playing in it? Impossible.
"If you don't love it, you don't last. You can't. The dream is what sustains you."
England Women's head coach Sarina Wiegman has paid tribute to Scott, telling englandfootball.com: "I must congratulate Jill on a very special career. I am so glad she was able to end on such a positive memory.
"It will be hard to imagine an England squad without her as she has been an icon of the team for so long. I respect her decision, but we will miss her positive impact on and off of the pitch for sure.
"To be able to play at the highest level for so long tells you how good a player Jill has been, and her story is a positive example that others will continue to follow. She still has a huge amount to offer, so I hope she won't be lost to the women's game in the future - whatever that role may be.
"She is a very special person, and although it was only for a short period, I feel privileged to have had the chance to work with her."
The FA have announced that they plan to honour Scott's career at one of England's home international fixtures in the autumn.