With just three more rounds of matches left to play, the victors would make themselves firm favourites to qualify for next year's tournament in Brazil automatically.
In preview to the encounter, Sports Mole has looked back on the six previous matches between the two nations, including video highlights.
England 2-0 Ukraine, May 2000
England went into this clash just hours after Kevin Keegan had named his squad for the upcoming European Championships. It also marked international debuts for both Steven Gerrard and Gareth Barry, as well as being Alan Shearer's last outing at Wembley as an England player. On the stroke of half time Ukraine goalkeeper Vyacheslav Kernozenko parried the ball into the path of Robbie Fowler and the Liverpool striker made no mistake from three yards out. The scoring was rounded off in the second half by Tony Adams, who found the net for the first time in England colours since 1988.
England 3-0 Ukraine, August 2004
A game that will live long in Shaun Wright-Phillips's memory, thanks largely to the fact that he scored an impressive goal on his debut. His strike was the third of the evening after Real Madrid teammates David Beckham and Michael Owen had given England a comfortable advantage.
England 2-1 Ukraine, April 2009
Fabio Capello's side made it five wins from five World Cup qualifiers, but only just. Peter Crouch continued his positive goalscoring record for England with a volleyed effort in the first half, but it appeared that the spoils were going to be shared when veteran AC Milan striker Andriy Shevchenko came off the bench to score with 16 minutes left to play. It was left to captain John Terry to seal the points for the Three Lions five minutes from time when he turned the ball in from close range.
Ukraine 1-0 England, October 2009
A night to forget for Robert Green, who became the first goalkeeper to be red-carded while on England duty. He was handed his marching orders in the 13th minute for a foul on Artem Milevskiy, but Shevchenko struck the post from the resultant penalty. The home side did make their numerical advantage count after 29 minutes, though, when Sergiy Nazarenko's deflected effort beat substitute keeper David James for the only goal of the game.
Ukraine 0-1 England, June 2012
Both sides went into this final group game with a chance of qualifying for the quarter-finals of Euro 2012, but it would be England who were celebrating at the final whistle. Wayne Rooney, who had missed the first two games of the competition because of suspension, was restored to the starting lineup by Roy Hodgson in Kiev and his headed effort from a Gerrard cross shortly after the restart was enough for England to go through as group winners, while co-hosts Ukraine were relegated to third.
England 1-1 Ukraine, September 2012
Visiting Ukraine would have returned to Eastern Europe after this meeting believing that they deserved all three points. They were much the better team for the majority of the game and took the lead in the first half courtesy of Yevgeni Konoplianka's strike. England applied the pressure in the closing stages, though, and got their reward late on when Frank Lampard scored from the penalty spot.