Bayern Munich have one foot in the Champions League quarter-finals after they beat Bundesliga rivals Bayer Leverkusen 3-0. (More Football News)
The Bundesliga leaders made light work of the team they are aiming to oust as champions at Allianz Arena, where Xabi Alonso's side were reduced to 10 men.
Bayern went ahead inside nine minutes on Wednesday, with Kane heading home from Michael Olise's right-wing cross.
A goalkeeping error from Leverkusen's Matej Kovar, as he dropped Joshua Kimmich's cross, allowing Jamal Musiala to tap home from point-blank range early in the second half.
Matters were made worse for the visitors when Nordi Mukiele received his second yellow card after fouling Kingsley Coman.
Kane then compounded Alonso's frustration, finishing coolly from the penalty spot after referee Michael Oliver deemed the England captain to have been held back by Edmond Tapsoba following a VAR review.
Having earned their first victory over Alonso's Leverkusen, Bayern will now head into next week's second leg with a significant advantage.
The winner of this tie will face Feyenoord or Inter in the last eight.
Data Debrief: King Harry strikes again
Kane has now scored 30+ goals in a season for the seventh time in his club career.
Since the first season he did so (2014-15), only Robert Lewandowski has more 30+ goal campaigns (nine) for clubs in Europe's big-five leagues.
With his double, Kane has now contributed to 48 Champions League goals. Among English players, only David Beckham (52) has registered more goal contributions in the competition.
