Montgomerie is an eight-time European number one
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Europe and America will combine for the first time against an international team in the inaugural Goodwill Trophy in China in November.
Scotland's Colin Montgomerie will be playing-captain of an eight-man team comprising players from the European and American 2006 Ryder Cup teams.
The international side will be led by South African Retief Goosen.
The format for the 13-14 November match will be foursomes on day one and singles to finish.
"It's a great opportunity to bring the Ryder Cup teams together for the first time," said Montgomerie.
"The Ryder Cup and Presidents Cup have proved that team golf works and people like to see it. It's also matchplay; we play a lot of strokeplay and it's nice to have a change."
Celtic Manor, where the tournament was announced on Friday during the Wales Open, will host the Goodwill Trophy in autumn 2007.
The 2006 Ryder Cup will take place at the K Club outside Dublin from 22-24 September.