Barry has been handed the skipper's armband because England coach Fabio Capello has allowed his recently reappointed captain John Terry to miss the match as a favour to Chelsea boss Carlo Ancelotti.
Terry, Frank Lampard, Ashley Cole, Wayne Rooney and Michael Dawson have been sent home by Capello to rest ahead of a busy period for their clubs, who are all competing in the Champions League, and that left Barry as the most senior players remaining in the squad.
Barry wasn't even in Capello's 18-man matchday squad for Saturday's 2-0 Euro 2012 qualifying win over Wales in Cardiff, but the absence of so many other experienced players made him the best captaincy option for the Italian.
"Barry will be the captain," Capello said at Wembley on Monday. "He played all the games with me apart from the last one.
"He is a good player and a good captain. Also he is the player with the most England caps."
Barry has some previous experience of captaining England. He took the armband for the second half of a friendly against Trinidad and Tobago in June 2008 and also had brief spells as skipper during friendly wins against Egypt and Denmark.