The Oscar-winning actress - who was born in Swansea, South Wales but is now based in Hollywood - will return to the country to take to the stage at Cardiff`s Millennium Stadium as part of the `Welcome to Wales` celebration to mark the beginning of the 2010 Ryder Cup golf tournament.
The `Chicago` star is hoped to bring the "glitz and glamour of Hollywood" to Wales as she opens the concert.
Opera artist Katherine Jenkins and male vocal choir Only Men Aloud will also perform at the concert.
Carwyn Jones, Wales` First Minister, said: "The whole of Wales is looking forward to The Ryder Cup, which will be a huge event for us.
"?Welcome to Wales` will be the ideal way to kick-start what will be a fantastic few days and will show the world the warm Welsh welcome that is awaiting visitors from all over the world."
In the past, Catherine - who has children Dylan, nine, and seven-year-old Carys with husband Michael Douglas - has attributed her foul mouth to her Welsh heritage.
She explained: "I`m from Wales, so I have a mouth like a truck driver!"
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