Kane, who also laid on two assists, now has 30 goals in his first season in Munich colours, equalling the record for a maiden campaign set by German legend Uwe Seeler for Hamburg in 1963-64. With nine games remaining to break the record, the England captain has also drawn nearer to the season record of 41 goals set by Bayern's Robert Lewandowski 2020-21.
The win was Bayern's second biggest this season, just behind their 8-0 demolition of Darmstadt in October. Bayern are now seven points behind Xabi Alonso's unbeaten Leverkusen, who host lowly Wolfsburg on Sunday. Having sealed their progression to the Champions League quarter-finals on Tuesday with a 3-0 home win over Lazio, Bayern were direct and decisive against Mainz.
Outgoing manager Thomas Tuchel said midweek Bayern needed to "win, win, win" to have any chance of catching Alonso's side and Kane obliged early, tapping in a Jamal Musiala pass after 13 minutes. Kane had a header saved seven minutes later, but Leon Goretzka was on hand to knock in the rebound.
Nadiem Amiri wove an incredible free kick through Bayern's defence shortly after but England striker Kane restored Bayern's two-goal lead in first-half stoppage time, collecting a lofted Goretzka pass on the turn and blasting home. Thomas Mueller added a fourth early in the second-half to break Mainz's resistance, allowing Bayern to run riot, with further goals to Musiala, Serge Gnabry, Kane and Goretzka to bring the tally to eight.
Kane, who arrived from Tottenham in the summer, also became the first player to score four hat-tricks in a Bundesliga season. The loss leaves Mainz in second last, nine points from safety. Elsewhere, RB Leipzig won 2-0 at home over last-placed Darmstadt to leapfrog Borussia Dortmund into
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