Charlotte Grimes, 24, was a finalist of ITV's Stars in their Eyes, where her performance of Cerys proved so impressive that the singer herself phoned up to talk to her.
Now Matthews, 33, is planning to appear at a charity concert with her sound-alike.
The singer last appeared on stage alongside The Stereophonics at a charity concert in London in April.
Since the band split up when Matthews was struck down by nervous exhaustion, she has also performed at the BBC Radio 2 Folk Awards and at a St David's Day musical celebration.
She is still reported to be considering the direction which she wants to pursue in her career.
The pair have spoken on the phone about their plans to sing a karaoke-style duet at a charity show in Cardiff in aid of a friend of Matthews, Louise James, who recently died.
The karaoke concert in aid of research into the protein-deficiency disease PSD - a hereditary blood-clotting condition - will take place at the Thistle Hotel on 8 September.
The concert will be a break for Matthews, who has been recording solo material in Nashville, after months off from singing.
Matthews said she felt strongly about supporting research into the disease which claimed her friend's life.
"It is the least I can do to try to get some reason for the death of Louise.
"I'm not sure if I'm going to sing any new songs, but I'll definitely be up on that stage.
"I telephoned Charlotte after her appearance. Two Cerys' - it's a scary prospect.
"But I'm sure anyone who comes along will have a lot of fun."
Charlotte said she was delighted with the concert, having first told Stars' host Matthew Kelly she would love to perform with her hero.
"I love Cerys and her music and I can't wait to sing with her," she said.
"I've spoken to her on the phone but haven't met her yet, so it will be absolutely brilliant.
"When the organisers phoned me and asked, I just thought: "Wow". It's a really nice idea.
"Cerys thinks it's really important to support this charity and I'm only too willing to help out. It will also be loads of fun!"
Matthews shot to fame with Catatonia, with hits including a duet with Tom Jones, Mulder and Scully, Road Rage and Strange Glue.
But the singer's hectic lifestyle took its toll and she quit from the limelight.