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Shortly after helping Europe clinch a nail-biting 14 1/2 to 13 1/2 win, Montgomerie revealed he had no plans to continue in the position for the defence of the trophy in Chicago in 2012.
"This is a one-hit time and I'm delighted that Europe have won. I will not be doing this again, I can assure you," Montgomerie said.
The 47-year-old Scot said he hoped his successor would emerge from the team of vice-captains who helped him plot Monday's win at Celtic Manor along with Spaniard Jose-Maria Olazabal.
Olazabal and Ireland's Paul McGinley are seen as the early front-runners for the prestigious post. "I think it's only right that it should be shared around," Montgomerie said.
As Europe celebrated regaining the crown they lost at Valhalla in 2008, Montgomerie was identified as the architect and driving force of the win.
The United States might have had a fighter pilot to give them a motivational speech but when it came to the heat of battle, Europe were led by a general who had left nothing to chance, player said.
"He educated everybody in what was going to happen, how it was going to happen, when it was going to happen, how he really wanted it all to pan out," English stalwart Lee Westwood said. "That's all a captain can do.
Montgomerie's decision to place US Open champion Graeme McDowell at the bottom of the singles order proved a masterstroke, the ice-cool Ulsterman anchoring Europe to victory amid excruciating tension.
"There's a reason why Graeme was there and it worked out brilliantly," Montgomerie said later.
"Colin has been inspiration putting this team together," was McDowell's verdict. "Just to be part of the Europe team this week has been a very special feeling.
Ireland's Padraig Harrington, a controversial wildcard choice by Montgomerie when many felt England's Paul Casey should have got the nod, said Europe's players had been determined to win for their captain.
Montgomerie, never beaten in eight singles matches as a Ryder Cup player, did not deserve to have his incredible record tarnished by being remembered as a losing captain, Harrington said.
"I know Colin says that it was all about the team and it is very much that way -- but I think we all knew how much this meant to Monty. He's done so well as a player, it is only fitting that he win as a captain," said Harrington.
"I think everybody on the team was aware that this was the one opportunity he would get to cap off an unbelievable Ryder Cup career, and we didn't want to let him down.
"Life doesn't always guarantee these things, but as a team, we wanted to guarantee that his captaincy would do his playing record justice, and it did."
Perhaps the most telling tribute came from Ian Poulter, one of the key figures of the victory who contributed with a crushing five and four victory over Matt Kuchar on Monday.
The outspoken Englishman was known to have a cool relationship with Montgomerie in the past, and was on record at being unhappy that both Casey and Justin Rose missed out on a wildcard this time.
However Poulter gave Montgomerie his seal of approval after the win.
"For Monty and all the assistant captains this week - they have been absolutely different class," Poulter said.
