The England captain struck twice in Bayern Munich's 4-0 win over Werder Bremen, reaching the landmark in just 104 appearances.
Kane's double moved him ahead of the milestones set by Cristiano Ronaldo and Erling Haaland, and his record-breaking night ensured Bayern continued their flawless start under Vincent Kompany.
"It is a proud moment to reach 100 goals for this club," Kane said after the match. "I have enjoyed every minute here, but the most important thing is that we keep winning as a team."
The striker was a constant threat from the outset, testing Bremen goalkeeper Karl Hein early on before Luis Diaz was credited with the opener after Jonathan Tah's clever flick.
Bayern's dominance grew when Kane converted his 18th consecutive Bundesliga penalty, setting a new top-flight record after being brought down by Marco Friedl.
Werder briefly threatened a response after the restart through Jens Stage and Yukinari Sugawara, but Manuel Neuer stood firm. Moments later, Diaz surged into the box and squared for Kane, who slid home his historic 100th goal to settle the contest.
Substitute Nicolas Jackson replaced him late on, denying him the chance of a hat-trick, before Konrad Laimer wrapped up the scoring with a neat finish.
Kompany praised his talisman, saying: "Harry is not only a goalscorer, he is a leader. Reaching 100 goals this quickly is incredible, but he is always focused on the team first."
The win stretched Bayern's unbeaten run to eight matches in all competitions this season, their best start since Carlo Ancelotti's tenure in 2016/17. With Kane in this form, Die Roten look ready to dominate both domestically and in Europe.
Bayern Munich have made a blistering start to the 2025/2026 season under head coach Vincent Kompany, whose side have rewritten European football history with a remarkable 16-game winning streak.
Germany coach Julian Nagelsmann has urged Bayern Munich's 17-year-old talent Lennart Karl to focus on development with the under-21 side before thinking about a senior national team call-up.
Bayern Munich's teenage winger Wisdom Mike has played down the growing media attention surrounding his rapid rise, insisting he is focused purely on improving his game and earning his place at the club.
VfL Wolfsburg have sacked head coach Paul Simonis after a woeful spell of six defeats in their last seven Bundesliga matches, leaving the club in 14th place and just one point above the relegation playoff spot.
