The Manchester United great, who has died at the age of 86, scored 49 goals in 106 appearances for his country.
Here, the PA news agency looks at five of the key games in Charlton's England career.
Scotland 0 England 4
April 19, 1958
Just two months after surviving the Munich air disaster, the shaken 20-year-old was handed his England debut. The former England schoolboys international capped his bow with a goal at Hampden Park in a comprehensive Home Championship triumph and felt guilty to be enjoying such moments, having emerged from the wreckage when others had not.
England 2 Mexico 0
July 16, 1966
Charlton scored a goal as impressive as it was important to get England's World Cup campaign up and running in 1966. Having been held to a goalless draw by Uruguay in their Group One opener, Charlton broke the deadlock in style against Mexico. He burst forward, jinked to the right and fired home a thumping 25-yard strike to set his side on their way to glory. Team-mate Terry Paine said Charlton's effort "was the best England goal I ever saw".
England 2 Portugal 1
July 26, 1966
The attacking midfielder put in a stunning, match-winning performance to earn England their only World Cup final appearance to date. Up against Eusebio-inspired Portugal in the semi-finals, the midfielder opened the scoring in the 30th minute after the ball fell kindly for him and struck home an emphatic second goal as the clock wound down.
West Germany 2
July 30, 1966
The 1966 World Cup final at Wembley earned Charlton and his team-mates their place in history. He impressed as a playmaker against the West Germans and hit a post with the scoreline at 2-2 in extra-time. The likes of hat-trick hero Sir Geoff Hurst grabbed the headlines, but Charlton still called the victory the "diamond of my days".
Northern Ireland 1
April 21, 1970
Bobby Moore gave Charlton the captain's armband as he celebrated becoming the second player in history to reach a century of England caps. It was a special moment made all the better by the fact he wrapped up the scoring in a 3-1 Home Championship victory at Wembley. Charlton called time on his England career following that summer's World Cup in Mexico.
Charlton’s death means Sir Geoff Hurst is the only survivor from England’s 1966 World Cup final win over West Germany.
Hurst said: “We will never forget him & nor will all of football.
"A great colleague & friend he will be sorely missed by all of the country beyond sport alone.”
England manager Gareth Southgate added: “One of our most iconic players, Sir Bobby Charlton’s impact on our only World Cup triumph is there for all to see.
“The world of football will unite in its sadness at losing an undisputed legend.”
England will pay a full tribute to Charlton at the European Championship qualifier against Malta at Wembley on November 17.