The Londoner, who reached a career high ranking of 48 in the world in 2009, won 20 titles on the ITF circuit and her best Grand Slam performance came back in 2008 when she reached the third round of the US Open.
She first became British number one back in 2003 and she held that honour seven times – most recently in July of last year.
She has also been a regular member of the British Fed Cup team.
However, she has struggled with injuries over the past few years and slipped outside the top 200 and she has now decided to quit the game to take up a position with BT Sport.
"I have given my decision a lot of thought and I believe this is the right time to move on to the next stage of my career," she said.
"I have had some magical moments along the way. I think I am leaving tennis in excellent shape with both Laura Robson and Heather Watson leading the way for Britain in the women's game."
Britain's Fed Cup captain Judy Murray added: "It's been a real pleasure for me to work with Anne as part of the Fed Cup team. You couldn't ask for a better, more committed team member.
"She's a great professional who represented her country with huge pride and passion. She's a fabulous role model for the young players and a lot of fun too. I'll miss her fashion advice as well as her presence but I'm sure she has a very bright future ahead of her."
- Sports & Recreation