The Manchester United striker is set to return to the Podgorica City Stadium for the first time since he was red carded for aiming a petulant kick at Miodrag Dzuzdovic in the 2011 meeting between the two sides.
And McClaren says the 27-year-old and his team-mates must show "emotional control" to overcome a similarly hostile atmopshere.
"Of course they can win the game, without a shadow of doubt and they’re capable of doing that," he told Yahoo!
"It’s a great test of their mentality, combating the outside elements like the atmosphere, fans and the on-field intimidation from playing these big European teams.
"We saw it in the last game with Rooney’s sending off, which has to serve as a lesson to the players. Every England player must be aware that to reach their potential, they have to play with emotional control, discipline and make sure England do not have to play a game with 10 men."
The former FC Twente coach went on to describe the Montenegrins as "dangerous" opponents, but expressed his belief that the hosts' temperament could let them down.
"They’re from eastern Europe, technically very good, fighters and always very passionate," he added.
|8/1||Mirko Vucinic is 8/1 with Paddy Power to open the scoring in Montenegro v England on Tuesday night
"When you play away the atmosphere is electric and England will have to deal with the noise generated by the home fans. They are very proud people and that passion feeds into the team.
"These kind of teams are very dangerous because technically and tactically they are very good. When you have that sort of passion, fight and togetherness, on the day it could be very difficult for England.
"It can however also work the other way, for example Montenegro could be too passionate or temperamental, they could go over the top and let themselves down. In many ways the game is not really about tactics, it’s about and controlling that emotion on both sides."
McClaren also highlighted Serie A stars Stevan Jovetic and Mirko Vucinic as the biggest threats to Roy Hodgson's side.
"Well they’ve got Jovetic and Vucinic; two strikers who are very dangerous," he said.
"Vucinic I’ve seen at Juventus, he does nothing in a game and then suddenly the ball will break and he’ll come to life and score a goal. That’s international football, you lose concentration for a split second and Montenegro could score a goal.
"They’ve done very well in the group, what I have liked and admired about them is they do not concede goals. They are very hard to beat, disciplined, organised and it will be difficult for England to score, but I think they are capable of doing that, providing they can deal with the intimidation on and off the field."
For more insight from Steve McClaren and other leading managers plus exclusive Premier League highlights go to www.yahoo.co.uk/sport