The players committee will meet during the Jan. 17-20 Abu Dhabi Championship to decide on the successor to Spain's Jose Maria Olazabal at the biennial team event, with 2011 British Open champion Darren Clarke and Ireland's Paul McGinley the frontrunners.
Clarke, however, said last month that he believes Europe should appoint a leader with a "huge presence", suggesting 2010 skipper Montgomerie should be considered.
"There's not a chance, after what he went through last time, that Colin would ever take the captaincy again," Harrington told Reuters in an interview.
"He puts so much more on the line than anybody else - it would be madness for him. He's had a great Ryder Cup playing career, he's been a successful captain - why risk all that?
"I can't see in any shape or form him agreeing to do it again."
The United States, desperate to halt a run of seven defeats in nine editions, appointed eight-times Major champion Tom Watson as captain last month.
"That was a big statement and brilliant for the event," said Clarke. "There are few more iconic figures in golf...and it sends out a statement they are serious about winning the trophy back.
"Maybe we have to consider other people. Whoever it is standing on that stage opposite Tom Watson needs a huge presence."
But Harrington, who won the British Open in 2007 and 2008 and the US PGA Championship in 2008, said half of Montgomerie's career would go out of the window if he lost as skipper.
"I had a long chat with Monty the evening we won the Ryder Cup in 2010," said the 41-year-old Irishman. "I could see the relief Colin had when he won.
"I don't think he quite realised until then the enormity of being captain for him. Most players who take the captaincy, whether they win or lose, it doesn't change people's perception of their overall career.
"Monty's career though is based on his eight order of merit wins and his Ryder Cup performances," added Harrington who has just signed a new multi-year deal with his club manufacturers Wilson Golf.
"By taking the captaincy he's putting far more on the line than anybody else because it would be hard to mention that he's unbeaten in the singles in the competition but, oh, he's also a losing captain as well. That would take the shine off his great record."
Harrington, a stalwart of six Ryder Cup campaigns, wants fellow-Irishman McGinley to take over as skipper at Gleneagles in Scotland next year before handing over to Northern Irishman Clarke for the 2016 version in the United States.
"Everybody's talking about it on the European Tour," said Harrington. "My own personal opinion is that McGinley should take it this time and for Clarke to do it in the US
"I think Darren would be a better captain in America because of his stature over there. McGinley would be a better option to go up against Watson.
"He can't match Watson in terms of his stature in the game - nobody can do that. The only way McGinley would tackle a Ryder Cup is to knuckle down and do his own business and organise things - he would be ideal for Gleneagles."
Harrington, who launches his 2013 European Tour campaign at next week's Volvo Golf Champions event in South Africa, said he had heard on the golfing grapevine that Watson was going to be named as US captain.
"That was the word, so it was no surprise when I found out he was appointed," said the genial Dubliner. "I had kind of heard earlier that they were going to do something different.
"I can understand it - they're not dominating the Ryder Cup and they need to bring in the heavyweight hitters to get the trophy back.
"They don't have the luxury at the moment of going through the ranks to pick the captain - they have to go right to the top of the pile and unless you pick Jack Nicklaus, there's no one else who carries the stature of Tom Watson," added Harrington.
"It will be fascinating for the US players because if you can learn anything from Tom Watson, anything at all during Ryder Cup week, it would be a career highlight."
- Sports & Recreation
- Darren Clarke