'The Celebrity Cup', to be filmed live over the August bank holiday weekend, will feature two teams of high-profile stars from Europe and the US, including Samuel L Jackson, Michael Douglas, Catherine Zeta Jones and Robbie Williams.
ITV was given first refusal to commission the programme made by Ant and Dec's independent production company Gallowgate, but turned the show down because 15 hours of golf was not considered "commercially viable" for the network and its advertisers.
An ITV spokeswoman said: "We thought the show was a great idea, but not for us. It would have taken up a lot of our schedule over a major bank holiday weekend."
Meanwhile, the tournament is a major coup for Sky One with its controller James Baker calling it one of the biggest television events of 2005.
"We are absolutely delighted that we have managed to secure one of the biggest TV events of the year," Baker said.
The two teams will play 'The Celebrity Cup' tournament over at the Celtic Manor resort in Wales, the venue for the 2010 Ryder Cup.
Potential players lined up for the US team include Andy Garcia, Sylvestor Stallone and Kevin Costner, with professional US golfer Mark O'Meara to oversee as the non-playing captain.
Potential European stars include Hugh Grant, Boris Becker, Catherine Zeta Jones, Frankie Dettori and Jodie Kidd, with Colin Montgomery taking a non-playing captain role.
Geordie duo Ant McPartlin and Dec Donnelly will not be allowed to present the show because of their "golden handcuffs" deal with ITV, but the pair will be allowed to appear as guests.
The show will be the first outing for Ant and Dec's Gallowgate, which is named after the area in Newcastle near where pair used to live.
'The Celebrity Cup' will be made in association with indie TWI, which makes BBC One's celebrity sports programme 'Superstars'.
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