The Sunderland forward, who scored his first international goal against Switzerland last month, was the fourth player to withdraw from the squad through injury after Aaron Lennon, Phil Jagielka and John Terry.
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Manager Fabio Capello, though, looked in relaxed mood at a news conference, re-arranging the tape recorders in front of him and joking "four, four, two" as he positioned them.
Peter Crouch will replace Bent alongside Wayne Rooney in attack and central defender Rio Ferdinand, playing his first competitive international for a year, will captain the side, taking the armband back from Steven Gerrard.
"Bent is out, he can't play and Crouch will play instead. There are enough options in the squad and he can play up with Rooney," Capello said.
SURPRISE CALL-UP
Bent's injury also increased the chances of a debut off the bench for surprise call-up Kevin Davies who is 33.
Ferdinand lost the captaincy when he pulled out of the World Cup squad due to injury.
"He was always going to come back as captain when he was fit," Capello said.
"I told Steve he was a fantastic captain and that he had to play like the captain tomorrow. But Rio was always going to come back as the captain when he was fit.
"I have watched Rio during training in the last few days and he is totally fit, he has played every game better and he is now at 100 per cent."
England unusually trained at Wembley on Monday morning, rather than Arsenal's training ground of London Colney, and went through their paces in glorious autumnal sunshine.
The pitch, severely criticised by Capello and others last season, looked in superb condition for the match, the first between the two countries.
Montenegro lead Group G having won their first three matches. England also boast a perfect start with victories over Bulgaria and Switzerland.
Capello said England must keep a close eye on Montenegro striker Mirko Vucinic, who celebrated his winning goal against Switzerland on Friday by putting his shorts on his head.
Vucinic, who plays for AS Roma, is well known to Capello from his days in Italy.
"He is very dangerous," Capello said. "He is their diamond flower."
