Wearing commemorative Nike boots having become the Three Lions' top scorer earlier in the week, Kane got Gareth Southgate's side off to a flying start.
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With spirits high following the 2-1 win over Italy, England didn't let Luke Shaw and Phil Foden's absence bring them down as they threatened to run riot in the first half.
After nearly poking home from close range just moments before his 37th minute strike, England's skipper opened the scoring after getting on the end of Bukayo Saka's cross.
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Getting ahead of his marker, Kane volleyed beyond Anatoliy Trubin as England took a deserved lead.
Kane's goal marks his 34th goal in 29 qualifiers and means the Tottenham star has now scored in four internationals in a row - a feat he hasn't achieved since he netted six in a row in 2019.
To honour Kane becoming all-time top scorer for his country, Nike unveiled a special pair of boots for the striker, featuring graphics of the England logos and a dedication to his daughter Vivienne and son Louis.
Just minutes after setting up Kane, Arsenal winger Saka then got on the score sheet himself.
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The Gunners forward whipped in a beauty into the top left corner after taking aim from outside the box.
Speaking on talkSPORT commentary, Stuart Pearce said: "A world-class finish. Back to goal, turned it onto his left and wowee, goalkeeper absolutely no chance.
"Curled right inside the far post, brilliant finish from a magnificent player who is getting better and better!"
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Should England see out the win on home soil, it'll be six points out of a possible six ahead of next summer's tournament, leaving them top of Group C.