Poulter and Montgomerie were involved in a public spat before last year's Ryder Cup, with Montgomerie implying captain Nick Faldo picked Poulter as a wildcard because they were friends.
However, Poulter added: "He will be able to perform under pressure because he always has - I can't see why he would be any different as captain and you'd expect him to get the best out of you."
Five-time Ryder Cupper Darren Clarke, who was part of the 15-man committee which unanimously selected Montgomerie, believes the Scot's superb record in the event made him the ideal candidate.
Montgomerie has won 23½ points as a Ryder Cup player, just 1½ points behind the record held by Nick Faldo.
"He's got an incredible record in the Ryder Cup, he's been the Ryder Cup talisman for many years," said Clarke.
"He'll be very player-orientated, he'll take a keen interest in how the players are doing.
Poulter's fellow Englishman Oliver Wilson said the fact Montgomerie is still a regular on the European Tour would prove to be an advantage.
Monty is the obvious choice - Gallacher
"I think the Ryder Cup committee thought certain people were out of touch, but Colin still plays and knows the players really well," Wilson, who made his debut in Valhalla last year, told BBC Radio 5 Live.
"He knows the guys' games, so preparation will be easier and everyone will feel comfortable dealing with him.
"There's nothing a captain can do out on the course, it's down to the players. But when you're playing against world-class opposition, if you get the pairings right you have a bit more confidence to do your job.
"A few mistakes were made in Valhalla, some of the pairings were not ideal. Certain players are made for foursomes because they're so steady, and others are made for fourballs because they're long hitters and make lots of birdies.
"Colin Montgomerie has a lot of experience, is very charismatic and will do a great job. He'll bring the team together and bring individuals belief."
Europe's 2002 captain Sam Torrance believes Montgomerie's love affair with the Ryder Cup will help his compatriot tackle what he concedes will be a tough job in Wales.
"It means more to him than any other event, and with his wealth of experience, he'll make a great captain," said Torrance.
Torrance applauds Monty choice
"Colin will do whatever is necessary with the players, whether it be bringing them down or picking them up. He'll do anything that is asked of him, and that's imperative."
Montgomerie will continue to play on the European Tour right up until the tournament, and Torrance believes that could help rather than hinder his captaincy.
"Colin has taken that decision and if he wins five tournaments then it would create no problems," said Torrance. "Instead, we'd just have a great player as captain."
Montgomerie, an eight-time winner of the European Order of Merit, will go up against Corey Pavin, who was named as the United States captain for the 2010 event in December.
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