Bayern Munich made a dream start to the new-look Champions League season, trouncing Dinamo Zagreb 9-2 at the Allianz Arena on Tuesday night.
Kane scored the opener from the penalty spot inside the first 20 minutes and got the Bundesliga side back on track with his second of the match, restoring his side's two-goal advantage after they conceded two quick goals early in the second period.
The England skipper went on to stick away a third and fourth for the night from the penalty spot in the 73rd and 78th minute, while Leroy Sane, Leon Goretzka, Raphael Guerreiro and Michael Olise also got on the scoresheet.
Kane becomes highest-scoring Englishman in Champions League history
Rooney's record of 30 goals in 85 top-flight European matches, which was the highest for an Englishman, was surpassed on Tuesday night thanks to Kane's stunning haul which took his tally to 33.
The England captain is already the all-time leading scorer for the England national team, a record which was also previously held by the former Manchester United striker.
Rooney scored 53 goals in 120 appearances for the Three Lions, while Kane has netted 68 goals and counting in just 100 matches.
Kane's four goals on Tuesday marked his highest tally in a single Champions League match and his second hat-trick in the competition, with the first coming in Spurs' 3-0 victory over APOEL Nicosia in 2017.
The Bayern Munich man also secured another record in the victory, becoming the first player in the history of Europe's top-tier cup competition to score a hat-trick of penalties in a single game.
Kane's impressive record in Europe
Kane only began his Champions League journey at the age of 23 for Tottenham, while Rooney debuted in the competition aged 18 for Manchester United against Fenerbahce.
During his time in North London, Kane notched up 21 goals in 32 Champions League games, but last season he scored more times in a single UCL season than ever before.
In 12 appearances before Bayern were knocked out by Real Madrid, Kane netted eight goals to end as the joint-top scorer in the competition alongside Kylian Mbappe.
Among current players, Raheem Sterling is the next-highest-scoring Englishman in the Champions League, with 27 goals to his name.
While still a Chelsea player, Sterling's season-long loan move to Arsenal means that he may be able to add to his tally soon if Mikel Arteta affords him the opportunity in Europe.