Gareth Southgate's side were in action at the Diego Armando Maradona Stadium for the first time since the World Cup and showed their quality in southern Italy.
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It took just 13 minutes for the Three Lions to take the lead through Declan Rice, who slotted home after the ball pinballed across the box.
Harry Kane then doubled their lead shortly before the break with a penalty that saw him become England's all-time leading goalscorer.
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The historic effort truly broke the spirit of the Naples natives as whistles greeted the Italian team as they made the long walk back to the dressing room.
Speaking during talkSPORT's commentary, Stuart Pearce said: "England are playing with a supreme confidence now.
"It's an arrogance if you like, a good arrogance at that."
But the boos appeared to inspire the home side with Mateo Retegui pulling one back on 56 minutes.
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Italy did push forward, leading to a nervy ending for England who finished the game with ten men.
This came after Luke Shaw was sent off following a strong challenge, leading Southgate's side to play the final nine minutes of normal time with a one-man disadvantage.
However England did manage to finish to job to earn their first win in Italy since 1961.
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