Their tournament kicks off on Sunday night against Serbia.
Bayern Munich striker Kane said: “I know what I am capable of. I know what I have done year after year. There is no reason why I cannot be the top scorer at this tournament.
“If we do well, I expect myself to be up there. To be scoring goals means I will be helping the team. That confidence is still there. I’m at my peak. Not just my physical peak. It’s also my mental peak, in terms of understanding the game, tactics and the space to run into.
“I am in a really comfortable place in terms of what I am capable of - but as always in these tournaments I will be judged on goals. So hopefully I will get a few.”
Kane added: “I think we're all at that stage now where we want to have a great tournament, want to make everyone proud - but we want to win. We've definitely had talented squads throughout my time as an England player.
“But I think what separates this one is how good everyone is playing leading up to this tournament. Phil was player of the year in the Premier League, Jude in La Liga, I had a decent season in the Bundesliga.
"I’m excited with this squad and to be leading them is a pleasure for me. I think we all just want to get out there and get started now.”