Baltacha, 30, reached a career-high ranking of 49 in 2010 but injuries and surgery saw her career tail off in recent years and she now sits outside the top 200.
"It just feels it's the right time," Baltacha said in a statement released by the LTA. "My body has taken such a bruising over the last 16 years and that's finally taken its toll.
"I have had some amazing experiences through playing tennis - some incredible highs and some very low lows - and I wouldn’t change any of them but now my mind and my body are telling me it’s time to move on to a new phase of my life."
Born in Ukraine, Baltacha moved to England as a child with her professional footballer father Sergei, who represented the USSR. The family later moved to Scotland, where Elena was raised.
In a 16-year professional career, Baltacha won 11 ITF singles titles and four in the doubles. She never reached a WTA Tour final, but her Grand Slam record includes three third-round appearances, twice in Australia and once at Wimbledon.
Other career highlights include victories over Li Na and Francesca Schiavone, who were both top-10 players at the time.
Her most recent success was an impressive victory in Nottingham earlier this season, which was her first final since winning the tournament in 2010.
Baltacha, who suffers from a chronic liver condition, said she intends to remain in tennis.
"I want to take that passion and put it into learning to be the best coach I can be so that I can take all my experiences as a player and use that to help develop the next generation of British tennis players," she said.
"I am very committed to my Elena Baltacha Academy of Tennis, which I started with my coach Nino Severino. We believe that no matter what background you are from, that all children, rich or poor, should have the opportunity to play tennis. Hopefully we’ll produce a champion one day."