"I will not in any way, shape or form come close to qualifying for the team. I am captain and very proud and honoured."
However, the eight-time winner of the European Order of Merit did add that if he continues to play he would fight for a place in the 2012 team.
Pavin was named as the United States captain for the 2010 event in December.
"He is someone I respect," Montgomerie said of his American counterpart.
"I've played three times in the Ryder Cup against him and managed to come out 2-1 at this stage.
"He is someone I respect and who holds the Ryder Cup without Tiger Woods playing on that occasion. Tiger will be back in 2010 so it will be very difficult and close."
In his eight Ryder Cups as a player Montgomerie helped Europe to victory on five occasions.
He has never lost a singles match and has a match record of 20 wins, nine draws and seven losses - giving him a total points score of 23.5, only 1.5 points behind the all-time record held by Nick Faldo.
Despite the impressive statistics, Montgomerie was not one of 2008 captain Faldo's wildcards for the Valhalla showdown, which Europe lost for the first time since 1999.
The Scot will be a popular choice in Wales, having supported the Celtic Manor Wales Open for several years, while also designing a course at the resort in Newport for owner Sir Terry Matthews.
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