The live programme, titled Freddie's World Of Sport, will launch on May 26 and run throughout the summer to August, also hosted by 5 Live presenter Mark Chapman.
Flintoff will appear on the station every Thursday between 8pm and 9pm to discuss the big stories and issues in the world of sport, as well as interview celebrity guests.
Freddie's World Of Sport will also specifically cover a range of major sporting events, such as Wimbledon, the Open Golf and England's test series against India.
Commenting on the new show, Flintoff said: "I've always been a fan of sport on the radio and can't wait to get started on Freddie's World Of Sport.
"We'll be talking to the biggest names in sport and getting the inside track on what's happening across the summer's sporting action."
Radio 5 Live deputy controller Jonathan Wall added: "We think Andrew's a really exciting addition to the 5 Live lineup. We love his enthusiasm for the new show and are delighted that he's chosen to start his live radio broadcasting career with 5 Live."
After retiring from cricket following the 2009 Ashes series, Flintoff has been busy carving out a media career for himself, including recent TV series Freddie Flintoff Versus The World on ITV4.