Setanta had signed a deal with Kentaro to broadcast the Group Six match live but the TV company went into administration in June, leaving the match without a broadcaster. All previously broadcast England matches have been available on television.
Fans who subscribe in advance will be charged 5 pounds to watch the match in Dnipropetrovsk which Ukraine need to win to maintain their hopes of qualifying for the 2010 World Cup. England have already clinched their place in South Africa.
"Over 20 million people in the United Kingdom regularly use the Internet to watch sport," Philipp Grothe, chief executive of Kentaro Group said in a statement.
"The mainstream adoption of broadband and the growing popularity of online viewing is now a realistic alternative to old-fashioned TV broadcasting."
He said Kentaro had also struck a deal to show the match across the country in cinemas.
Previous England matches have been available on free-to-air or cable television and England's home qualifiers are shown on terrestrial television.
England fans' groups have criticised the decision to show the match exclusively on the Internet but the FA stressed on Monday that it had no authority over the match with the rights being sold by the Ukraine FA and their commercial agents.
"We would obviously like to see the game broadcast to as many people as possible," FA spokesman Adrian Bevington told the BBC. "These are the rights of the Ukrainian FA and the agents they've appointed to sell them.
"A traditional TV platform would be ideal to broadcast the game but it's not the case. It's not in our control."
Former England manager Sven-Goran Eriksson will be a co-presenter of the coverage which will also be available through the websites of several national newspapers.
