The 46-year-old, who had an ill-fated stint on ITV's breakfast show Daybreak and fronts its football coverage, will present Friday night Drive on Radio 5 live.
Chiles, who presented Wake Up To Money on the station when it was set up in 1994, said it was exciting to be returning.
He added: "It was a privilege to have been there right at the beginning and I'm thrilled to have been asked back. It'll be great to tackle news, current affairs and business stuff, as well as sport."
He will co-host Drive with Anna Foster, with regular presenter Peter Allen continuing on the show from Monday to Thursday.
The BBC also announced that Christian O'Connell, Jonathan Pearce and Matt Johnson will share presenting duties on 5 live's Fighting Talk show after presenter Colin Murray left the station.