Gareth Southgate revealed he decided to give Kane the armband after seeing his leadership qualities on their boot camp training with the Royal Marines.
England boss Southgate insists he is in no rush to appoint a permanent successor for Wayne Rooney but believes that the Tottenham striker can lead them to victory against the old enemy.
It is the first time Kane has been available to play for Southgate and the manager said: “I’ve spoken before about developing more leaders in the group.
“That’s been key and was evident this week with the different things we’ve done. Harry’s not been with us up to this point. His mentality is excellent. He has a very good view of the game. He’s keen to lead.
“At the moment I’m not looking beyond tomorrow. It’s been a natural fit this week, but I’m not in a rush to make a (long-term) decision. The key is to develop the group of players and show them they’re capable of leading.
“Everyone says we don’t have leaders. That’s not my view of this group of players, but they have to step forward at different moments and show it. He was very chuffed, the significance was not lost on him and it’s a great honour.”
Kane added: “Any player growing up as a footballer dreams of being England captain one day and I am no different.
“I’ve been captain for Spurs a few times. You wear an armband and it gets built up a lot.”
Southgate also urged his players to follow the example set by England’s under-20s who have reached their World Cup final on Sunday.
He added: “It’s brilliant for youth development in our country. Everybody knocks youth development.
“Everyone says we don’t have good youth development, and people search the world to bring people in when players are there under their noses. There’s a lot of talent. Hopefully the world will see what is happening there.”