Gareth Barry will wear the captain's armband when England take on Ghana at Wembley on Tuesday evening.
Coach Fabio Capello released the five players who featured in the 2-0 win in Wales who also have Champions League duty next week, which means skipper John Terry, Frank Lampard, Ashley Cole, Wayne Rooney and Michael Dawson have all returned to their clubs.
Terry's absence means Capello had to give the armband to another player just days after the Chelsea defender returned to the role on a permanent basis. With Lampard and the injured Rio Ferdinand and Steven Gerrard, who have recently captained England, also not in the squad it meant Capello had to look elsewhere.
The favourite to lead the team against the World Cup quarter-finalists was always Barry, who was not even in the 18-man squad at the Millennium Stadium.
Barry has worn the armband twice in the past, taking over from Steven Gerrard and Frank Lampard respectively when they were substituted in international friendlies against Egypt and Denmark.
"He's a good player, a good captain,'' said Capello. "He's also the player with the most England caps.''
Capello will use the game to experiment with fringe players and revealed he will make seven or eight changes to the side which started on Saturday. Andrew Carroll, Leighton Baines, Gary Cahill and Phil Jagielka are confirmed starters but Scott Parker, who played so well in Cardiff, is carrying a knock and will be assessed. But on Monday, Glen Johnson was the only absentee from training of the 20 players still at Capello's disposal.
"If Parker is fit he will play,'' he added. "He's got some little problem but I hope he will be fit.
"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.
"The players that aren't here, those that went home, are not here because if you are tired it is easy to be injured.
"I decided the five players to let go because they had just played four games in 10 days. I respect the players and the clubs and I have done this because the players are important for the national team and the clubs. The players in the Premier League are only playing three games, not four. This is a big difference.
``It will be a really interesting game for the fans. These matches are important for a manager to understand the value of some players. When you play here, at Wembley, it is really important to understand what happens because the England shirt is really heavy. Also, if some important players are injured, I will know who the substitutes should be.''
Barry backed Capello's decision to release five senior players, although he admitted he could understand fans' disappointment.
"I can certainly see the reasons for (Capello's) decision,'' Barry said. "It's a tough part of the season, there are good reasons why the players were let home. There will be a few players chomping at the bit to take their chance.''
"The fans have bought their tickets to maybe see certain individuals play for England, but the players selected were in the 26 from the start.''
On being named captain, Barry said: "It's obviously going to be a massive moment in my career, a proud one. I'll be the same player as I always am. You don't put the armband on and change.''
The Manchester City midfielder claimed he was not thinking about whether being named captain made up for being left out of the team to face Wales.
"I'm not trying to look at it in that sort of way, that's gone now,'' he said. "I was obviously disappointed not to be involved, but two days later I am being asked to lead the country out.''
Ghana are likely to ring the changes too, having beaten Congo 3-0 on Sunday in an African Nations Cup qualifier with the goals coming from Prince Tagoe, Dominic Adiyiah and Sulley Muntari.
Meanwhile, Gerrard has revealed that Capello phoned him to explain the captaincy situation. The Liverpool skipper led England at the World Cup finals with Ferdinand ruled out of the tournament.
He said: "I did get a call. The manager just explained what he had been doing. He didn't have to. The manager's paid to make big decisions and he's made the decision. We all have to respect it and move on.
"The captaincy's very important, I know what it means to John and he's been frustrated since he lost it. Everyone's obviously upset for Rio but pleased for John, and as a player being in the middle is difficult."
Capello has also admitted that England made a mistake over Rooney's disciplinary situation, with the coaching staff failing to warn the striker that he was one booking away from a suspension. That now means he misses the important date with Switzerland at Wembley on June 4.
Capello said: "Usually we tell players but this time no. Rooney misses the next game and when I told him he said 'Why?' He was surprised. He didn't realise he'd been booked before.
"Rooney wants to win every tackle and I changed him in the second half because if he had got another yellow card he would have been sent off."