The two sides, along with Ukraine, are separated by one point at the top of their qualifying group with two matches remaining.
A win for Montenegro on Friday would mean that the outcome of the group would be decided in the final round of games on Tuesday, when England take on a Poland side who sit three points behind Roy Hodgson's men.
But a victory for England, and defeat for Ukraine in Poland, would leave Roy Hodgson's men in a position of strength, with their goal difference considerably stronger than Poland's.
|11/1||England are 11/1 with William Hill to beat Montenegro 3-1
In their first showdown in the group the match ended 1-1, with Wayne Rooney scoring early for England only for Dejan Damjanovic to level with 14 minutes to play.
Should England qualify it would be their 14th appearance at the World Cup finals, while Montenegro are eyeing their debut on football's biggest stage in Brazil next summer.
England have not lost a competitive fixture since they were beaten by Germany in Bloemfontein in 2010, although they were eliminated from Euro 2012 on penalties after a goalless draw against Italy at the quarter-final stage.
Hodgson will be without Ashley Cole for the two fixtures after the Chelsea left-back pulled out with a rib injury. Arsenal's Kieran Gibbs has been added to the squad but Leighton Baines is poised to start in defence.
After missing England's last two qualifiers against Moldova and Ukraine with a thigh injury, Daniel Sturridge could be in line to return after scoring six goals in seven Premier League games for Liverpool this season.
Montenegro have not won any of their last four matches, but only one of those ended in defeat – 4-0 against Ukraine in June – and coach Branko Brnovic remains confident heading to London.
"We can do it," he said. "We have the quality and this team play much better away than home.
"I believe that my players do not need any special motivation for such games, because to play against the great England team at Wembley is something that every player dreams about."