The Montenegrins, who first played as an independent nation in the 2010 World Cup qualifiers, will seal a play-off berth if they beat England and if Switzerland, who are also eyeing a runners-up finish, fail to beat Wales.
England top the group with 17 points from seven games ahead of their final game with Montenegro, who have 11 from six, meaning that Fabio Capello's men need a draw in Podgorica to clinch a place in next year's finals in Poland and Ukraine.
Third-placed Switzerland, who are away to Wales on Friday and at home to Montenegro on October 11, have eight points from six games and will get a play-off berth if they win both their remaining matches.
"Although it may not be the decisive match in the qualifiers, the clash with England is the game of the decade for us because we don't play teams at that level very often," Jovanovic said on Monday after coach Branko Brnovic named his 27-man squad.
"We are all confident that we can get a result which would leave us in contention for a play-off berth.
"We know it's likely it will go down to the wire, meaning our last game away to the Swiss, so we are taking it one game at a time aware that we have to produce our best football in both encounters," said the Spartak Nalchik left back.
Montenegro made a bright start, winning their opening three games and then earning a 0-0 draw against England at Wembley before a home draw with Bulgaria and a 2-1 defeat in Wales forced coach Zlatko Kranjcar to step down last month.
His replacement Brnovic, a former Yugoslavia midfielder, will be buoyed up by having his team back to full strength after Fiorentina striker Stevan Jovetic quickly hit top form after recovering from a long-term injury.
Juventus striker Mirko Vucinic should partner Jovetic up front while Manchester City defender Stefan Savic is expected to reproduce his effervescent Wembley performance.
"Our strikers are in good form and the whole team will play their hearts out because this is a great chance to get Montenegro on the big stage," said Jovanovic.
Europe's nine group winners and the best second-placed team will qualify automatically for the finals while the other eight runners-up enter two-leg play-offs for the last four berths.
Squad:
Goalkeepers: Mladen Bozovic (Videoton), Srdjan Blazic (Panetolikos), Miodrag Todorovic (Mogren Budva)
Defenders: Savo Pavicevic (Maccabi Tel Aviv), Elsad Zverotic (Young Boys Berne), Drasko Bozovic (Buducnost Podgorica), Milan Jovanovic (Spartak Nalchik), Luka Pejovic (Jagiellonia), Marko Basa (Lille), Stefan Savic (Manchester City), Miodrag Dzudovic (Spartak Nalchik), Radoslav Batak (Mogren Budva), Vladan Adzic (Rudar Pljevlja).
Midfielders: Nikola Drincic (Krasnodar), Mladen Kascelan (LKS Lodz), Milorad Pekovic (Greuther Furth), Mitar Novakovic (Amkar Perm), Vladimir Bozovic (Rapid Bucharest), Simon Vukcevic (Blackburn Rovers), Petar Grbic (Olympiakos Piraeus), Marko Cetkovic (Jagiellonia).
Forwards: Stevan Jovetic (Fiorentina), Dejan Damjanovic (Seoul), Mirko Vucinic (Juventus), Radomir Djalovic (Amkar Perm), Andrija Delibasic (Rayo Vallecano), Fatos Beciraj (Dinamo Zagreb).
