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The Welsh singer will present the 1pm to 4pm daily lunchtime slot while the regular host is on maternity leave. Matthews has previously deputised on the station and currently hosts her A Month Of Sundays show for the broadcaster.
"It’s been 20 years since I first started in music, and these last few months hosting shows for 6Music have been as exciting as ever," she said.
"I get to play lost gems from my record collection as well as choose new music, and on top of that, there's live music in The Hub and weird and wonderful guests to meet.
"Seeing the responses streaming back in via text and email from the listeners is simply addictive and to have this experience on a daily basis will be an absolute pleasure."
BBC6 Music controller Bob Shennan added: "Cerys's amazing passion for music delivered in a charmingly engaging way is a welcome addition to 6Music and will provide the perfect lunchtime cover whilst Nemone is away."
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