Murray skipped the singles in his final appearance at Wimbledon this month after having surgery to remove a spinal cyst in late June, but was initially entered in singles and doubles, alongside Dan Evans, in Paris.
However, he has now announced his decision to only play doubles in the final event of his career due to his fitness issues.
"I've taken the decision to withdraw from the singles to concentrate on the doubles with Dan," Murray said in a statement.
"Our practice has been great and we're playing well together. Really looking forward to getting started and representing GB one more time."
Murray won singles gold at London 2012, beating Roger Federer in the final, and successfully defended his title in Rio four years later by defeating Juan Martin del Potro.
He also has a mixed doubles silver from London partnering Laura Robson.
The three-time Grand Slam winner said on Tuesday he would retire after the Paris Games, where the tennis tournament runs from July 27 to August 4 at Roland Garros.
Murray, who revived his career after having hip-resurfacing surgery in 2019, said it was the right time to bow out.
"I didn't feel that way a few months ago when I thought this was when I was going to stop," Murray said.
"I didn't really want to, whereas now I want to and I know that it's the right time for me."
