The Bayern Munich striker makes his 126th appearance for the Three Lions, surpassing the previous mark held by Peter Shilton between 1970 and 1990.
Legendary goalkeeper Shilton and Prince William made a presentation to Kane on the pitch at Wembley Stadium ahead of the game.
The feat comes just weeks after Kane was crowned the first English winner of the Ballon d'Or in 25 years.
Kane made his England debut in March 2015 in a friendly against Lithuania and scored his first goal just 79 seconds after coming off the bench.
The 33-year-old has scored 91 times for England and is the country's leading scorer, with Wayne Rooney trailing him way back in second with 53 goals.
Kane was named the best player in the world at a ceremony in London after a stellar campaign in which he scored 61 goals in 51 games for Bayern.
He also netted 12 times for England, six of which came at the World Cup in the summer, as Thomas Tuchel's men finished in third place.