Launching this Sunday, the chart will be presented by Melanie Sykes and Heart 106.2's Nick Snaith at 4-7pm.
'The A-List' will be aimed at a mature audience of 25- to 45 year-olds and will offer listeners a more "relaxed feel" in comparison with other more faster-paced charts. It will include a mix of lifestyle chat, celebrity interviews, entertainment news and contemporary music.
The show will be the first UK chart to focus on the biggest-selling artists rather than the biggest-selling tracks.
Christina St Croix, Baileys GB brand manager, said: "The mix of lifestyle chat with an artist-led chart will epitomise the contemporary and easy-going attitude of Baileys."
'The A-List' will be managed by Hit40uk and produced by UBC Media. It is to be broadcast across 50 radio stations, including Heart, Real Radio and Century Networks.
Rob Corlett, managing director of Hit40uk, said: "Baileys is a fantastic brand for the 'The A-List' and we are delighted that it is on board."
The chart will be compiled from airplay statistics, album and single sales (including downloads), and music DVD sales.
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