The Scot, who was a victorious captain of the European team at Celtic Manor two years ago, believes that the winners are determined by who can handle the pressure the best.
"I was trying not to [let emotion creep in], but it's very difficult not to," said Montgomerie, speaking on his role as a pundit for Sky Sports News.
"I was trying to make decision as fact, [considering] greens and fairways in regulation, but that flies out the window on the first tee, because it's all about emotion.
"Forget how you played in practice and what's happened before, it's all about how you handle what is about to happen."
Montgomerie was unbeaten in singles matches in Ryder Cup competition.