She was a founding member of Welsh rock band Catatonia and a leading figure in the "Cool Cymru" movement of the late 1990s.

[17] Matthews joined the Pet Shop Boys on the Pyramid Stage at Glastonbury in June 2000, performing a duet of their hit "What Have I Done to Deserve This?".

During September and October 2006, Matthews embarked on a UK and Ireland tour, during which she played tracks from her first two solo albums as well as three Catatonia hits.

She was voted off one day before the final episode, coming fourth behind Jason "J" Brown, Janice Dickinson and eventual winner Christopher Biggins.

She performed the Bonnie Tyler hit "Total Eclipse of the Heart" and the Dolly Parton/Kenny Rogers duet "Islands in the Stream" along with Terry Hall and the BBC Concert Orchestra.

In an interview on the eve of the launch of her Welsh mini-album Awyren = Aeroplane, Matthews confirmed she had divorced from Riddle and temporarily moved back to her farm in Pembrokeshire.

Matthews joined the Welsh band Manic Street Preachers onstage at The O2 on 28 February 2008 to sing the female vocals of their 2007 hit "Your Love Alone Is Not Enough" as part of the NME awards celebrations that year.

[29] From November 2008, Matthews sat in for Stephen Merchant and Marc Riley on BBC 6 Music and went on to present George Lamb's slot in April 2009.

It was recorded in Providence, Rhode Island, Nashville, Seattle and London, and coincided with a two-week UK tour in October.

She frequently contributes to BBC Radio 4 programmes such as Feedback, Frontrow, Loose Ends and Saturday Live, also writing a column for world music magazine Songlines.

[33] They included "Calon Lân", "Cwm Rhondda", "Migldi-Magldi" (sung as a duet with Bryn Terfel), "Myfanwy" and "Sosban Fach".

[36] In April 2011, a video was released through Matthews's official YouTube Page[37] of the lead single from Explorer, "Sweet Magnolia".

Matthews played the Isle of Wight and Hay festivals in 2012, the latter with a Woody Guthrie tribute show, and collaborated with artists such as Arun Ghosh, Tunde Jegede, Attab Haddad, Frank Moon and the London Bulgarian Choir.

2012 also saw Matthews play music from her collection of Welsh traditional songs Tir, with Ballet Cymru, ending in a show in Sadler's Wells, and a nomination for a Theatre Critics Award 2012.

[39] Matthews played UK literary festivals including Dartington, Chester, Hay and Edinburgh and released an album of traditional Welsh reels and songs, Hullabaloo.

She sang Patsy Cline's "Crazy" and Dylan's "Blowin' in the Wind" as part of the memorial service for esteemed War correspondent Marie Colvin, in May 2012.

Also in 2012, Matthews appeared as a celebrity guest mentor for Tom Jones's team on the first series of the UK version of The Voice.

It is a festival which celebrates the great outdoors, with abseiling, campfires, axe throwing, foraging, talk on survival, as well as cultural activities, crafts, books and music.

[42] Matthews won a "St David Award" – for her contribution to culture in 2014 – run by the Welsh government, in its inaugural year, 2014.

[48] In 2022, Matthews made a pilot for a new BBC Radio 4 music programme called Add To Playlist, with Jeffrey Boakye.

This emerged as a weekly Friday night show which Matthews and Boakye present and direct musically, production is by Jerome Weatherald.