The 30-year-old Manchester City man is handed the armband by coach Fabio Capello just days after John Terry was reinstated as skipper following a year's punishment against Wales at the weekend.
A number of players will be rested for the clash with the Black Stars at Wembley including Terry, as Rio Ferdinand and Steven Gerrard are still missing through injury.
It will therefore be a much-changed Three Lions side with Frank Lampard, Ashley Cole, Wayne Rooney, Michael Dawson and Kyle Walker all returning to their clubs.
Capello confirmed that others now have the chance to step up to the plate, and Liverpool striker Andy Carroll is set to start.
On Barry's appointment, the Italian said: "He's a good player, a good captain.
"He's also the player with the most England caps."
Bolton defender Gary Cahill and Everton duo Phil Jagielka and Leighton Baines will start the tie in defence, while Scott Parker faces a late fitness test.
"Some of the players have played a lot," Capello added. "They should only play three games in eight days - I think four games in 10 days is too much. I respect the clubs and the players.
"I'm not sure but it might be seven changes. Joe Hart will play in goal, I will play Cahill, Jagielka centre-backs and Baines on the left. I will play Andy Carroll and Barry will be the captain.
"If Parker is fit he will play. He's got some little problem but I hope he will be fit."
Capello insisted fans should not feel short-changed by his changes, claiming fringe players will benefit from experiencing the 'spirit of the team'.
"I respect the fans," he said. "It will be interesting for the fans to see some players they know very well, it will be interesting for me and for the fans.
"The players who will play will be really good players, it's really important for the players to understand the spirit of the team and I hope tomorrow we can see the spirit on the pitch like in the first 30 minutes against Wales."
However, the England coach also admitted that he has respect for the players and clubs following the many withdrawals.
He said: "I respect the players, I respect the clubs, and I want the players to be fit after this game."