The contemporary chart show, called The A-List, will be presented by Melanie Sykes and Heart 106.2's Nick Snaith, and will air across 50 stations including the Heart, Real Radio and Century networks.
The new chart show is aimed at a mature audience, with a combination of lifestyle chat, celebrity interviews, entertainment news and adult contemporary music.
It is designed to offer listeners a more "relaxed feel" and will reflect the tastes of an audience of 25 to 45-year-olds.
The A-List will be managed by Hit40uk and produced by UBC Media. It will air on Sundays from 4pm to 7pm.
The one-year sponsorship deal with Baileys was negotiated by Carat.
Christina St Croix, brand manager, Baileys GB, said: "The unique mix of lifestyle chat with an artist-led chart will epitomise the contemporary and easy-going attitude of Baileys."
The A-list rankings will be decided by airplay statistics, album and single sales (including downloads) and music DVD sales.
A new dance and urban chart, Fresh 40, set to launch in the spring is looking for a similar sponsor. Woolworths currently sponsors the Hit40uk chart.