Michael Owen was the last player from England to receive the prestigious individual accolade in 2001, but Kane's incredible 73-goal haul last season for club and country earned him the award from French magazine France Football.
Bayern Munich forward Kane was a popular winner in the capital on Monday night (Tuesday AEDT) and has followed in the footsteps of Stanley Matthews, Bobby Charlton, Kevin Keegan and Owen.
Barcelona and Spain's Lamine Yamal and Real Madrid's French forward Kylian Mbappe provided strong competition for Kane and the trio were bizarrely announced as winners on the official website hours before the ceremony.
Further chaos followed with the awards pushed back by 30 minutes to start at 8.30pm (local), but just over two hours later and Kane received the 70th Ballon d'Or to enormous cheers and chants of 'Harry' inside the London Palladium, minutes after London City midfielder Alexia Putellas claimed the women's prize for a third time.
The 32-year-old midfielder Putellas ended Spain teammate Aitana Bonmati's three-year reign by winning her third Ballon d'Or Feminin.
"Wow, I'm almost speechless," an emotional Kane said on stage.
"First of all, thanks again to France Football and the Ballon d'Or for this amazing event. Being in London, it is extra special, it felt like a good omen.
"Thank you to everyone for voting for me. I can imagine it was very tough. Thank you to everyone that voted for me."
Kane, who thanked England, Bayern and former club Tottenham, added: "It's just the journey. For any young boy or girl who wants to achieve their dream, anything is possible.
"I hope my journey, it wasn't straightforward, I didn't go straight to the top, I had to experience a lot of loan moves and fight my way to get to where I am now. I hope that can give you inspiration and thank you very much."
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