The DJ will interview previous Breakfast Show hosts such as Tony Blackburn, Sara Cox, Zoe Ball and Steve Wright on the 60-minute BBC Two programme. Moyles has hosted the Breakfast Show since 2004, which is the longest ever stint in the popular slot.
"Millions and millions of people have grown up listening to the Radio 1 Breakfast Show, it's been on everyday for over 40 years," said the 36-year-old.
"Everyone between the ages of 8 and 80 will have heard it at some point - it's massive."
Executive editor of BBC Entertainment Katie Taylor said: "We're thrilled to have Chris on board to unearth the real story behind the early morning antics of some of his most legendary predecessors.
"He will be exploring a subject that so many viewers will have their own memories of, across a variety of eras, sparking feelings of nostalgia in homes all over the country."
When Moyles Met the Radio 1 Breakfast DJs will air on BBC Two later this year.