Kane will get a rest as the Three Lions take on Greece on Thursday during this period of international matches.
Kane has been in fine form this term, scoring ten goals in nine games for Bayern Munich.
In his absence, John Stones will be getting the armband for the game.
“(It's) definitely everything that I could have dreamed of as a kid,” Stones said.
“More for my family, I think.
“To be able to see me walk out as England captain is a special moment and one that I can't thank Lee enough for.
“It was a great conversation that we had last night and one that I was a bit speechless in.
“But an incredible moment for me and it's a bit more normal actually today, everything resumes as normal: the preparation, the training that we've done and our focus is the same.
“To be walking out with the armband on is an absolute honour and one that I'll cherish forever.”