Montgomerie believes all 12 members of the United States team will relish the chance of claiming McIlroy's scalp if they are drawn against the British Open and U.S. PGA champion in the foursomes, fourballs or singles matches.
"Rory is the one player that America wants to play because they've nothing to lose," the 51-year-old Scot told the Daily Express newspaper on Monday.
"It was a bit like that for us against Tiger. When we did draw him we would say 'Game on, I've got a chance here.
"If he beats me he's supposed to beat me, if he doesn't, well, what a day for me and what a day for the team."
Montgomerie, who also featured in eight Ryder Cups as a player, said European captain Paul McGinley may be tempted to "hide" McIlroy in the opening foursomes or fourballs on Friday and Saturday.
"I think a lot of pressure is on Rory's shoulders," explained the eight-times order of merit winner. "If the rest of the team see Rory winning it gives them confidence.
"If the team see Rory losing in one of the first groups then it's difficult to think 'we've got to pick up the pieces' so it's a huge temptation to hide him away.
"You don't want to put your main star out at number one because the rookies in the American team can play and any one of them can score a 66 and win," said Montgomerie who is Europe's third highest Ryder Cup points scorer of all time with 23 1/2.
"I would definitely be for hiding Rory the way Tiger was many times. We expected him at number one in the singles in 2006 for instance when America were well down at the K Club and he turned up at number four."
(Reporting by Tony Jimenez, editing by Sudipto Ganguly)
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