When Kane leads England out at Wembley to earn his 126th cap, he will surpass the previous record held by former goalkeeper Peter Shilton since 1990.
It will be the latest landmark moment in an incredible 12 months for the Bayern Munich striker, who became the first English player in 25 years to win the Ballon d'Or in October.
The 33-year-old Kane is also England's record scorer with 91 goals, as well as holding Tottenham Hotspur's all-time mark with 280.
Since leaving Spurs to join Bayern in 2023, Kane has taken his game to another level.
He has amassed 156 goals for the German club, finally winning the first silverware of his career with Bundesliga titles in 2025 and 2026.
But breaking Shilton's long-standing record also matters to Kane, who told a pre-match press conference on Wednesday: "It's definitely up there as the biggest (achievement).
"I think it showcases consistency at the highest level. Testament to all the dedication, the time people don't see, that keeps me fit and healthy. This is one of the biggest milestones in my career."
For all Kane's brilliance, England have not won a major men's international trophy since lifting the 1966 World Cup on home soil.
And Kane suffered fresh frustration in July as England were beaten by Argentina in the semi-finals of the World Cup.
Chasing century
England were leading 1-0 until late in the game but could not score again, with manager Thomas Tuchel criticised for packing the team's defence, only for Argentina to score twice late on as Kane was denied a first appearance in a World Cup final.
"In terms of what's next, I don't like to put limits - 100 goals (for England) is a milestone to reach as soon as possible," added Kane.
"We've done extremely well in tournaments, going into latter stages. I'm feeling really good, and hopefully there will be many more years to see what I can achieve."
Tuchel, speaking earlier Wednesday, was coy when asked if Kane was England's greatest footballer.
"I don't know. He's up there, of course. It's now proven. It's always nice if things are proven in sports - he has his prizes and records, he will build on these records, score more goals and get more games.
"Tomorrow he will start for us as captain. It's a big occasion to present the Ballon d'Or trophy to our fans and have it embedded in the same day he gets his all-time record for 126 matches, it's a beautiful occasion."
The German added: "It would have made it even more obvious he should win it (if England had won the World Cup). But he stood up, and you see him as a proper man, well-dressed and speaks so well-educated, then you know the prize is in good hands."
