Socceroos defender Trent Sainsbury had a UEFA Champions League debut to forget as a deflection off the Australian defender helped Tottenham Hotspur to a stunning 2-1 comeback against Group B rivals PSV.
Spurs appeared to be doomed as they trailed for much of the Group B match, but they turned things around late on to capitalise on the Italian side dropping points at home to Barcelona.
An early Luuk de Jong header forced Spurs to throw caution to the wind and they racked up 30 shots, but, for the most part, they came up against an inspired goalkeeper in the shape of Jeroen Zoet.
Spurs' pressure eventually told in the 78th minute as Kane got the equaliser and he then had a major role in the winner as Sainsbury deflected the England striker's header past the despairing Zoet, teeing up Mauricio Pochettino's men nicely for two huge clashed with Inter and Barcelona.
Spurs were trailing after 61 seconds as De Jong rose highest in the penalty area after losing Dele Alli and sent an unstoppable header into the bottom-left corner.
For the rest of the first half the home side were dominant, but Zoet in PSV's goal was in fine form, making a brilliant double save to deny Christian Eriksen and Alli in the 28th minute.
Alli was thwarted again just before the break, with Zoet acrobatically getting down to his right and pushing the shot away.
Spurs remained the controlling force after the restart, but they almost found themselves two behind in the 58th minute – Paulo Gazzaniga crucially stopping Gaston Pereiro's goal-bound header from a corner.
PSV's resistance was finally broken Kane found the bottom-right corner with a left-footed strike following a Fernando Llorente knockdown.
Kane was to the fore once again in the dying embers of the contest, his headed attempted clipping Sainsbury on its way into the net to leave PSV on the brink of elimination.
What does it mean? Do or die against Inter
Following late drama in both Group B matches, Inter's trip to Tottenham at the end of the month suddenly takes on even more importance. Victory for Spurs in that game will leave both teams on seven points with a match to play.
Winks a star in midfield
Kane was the hero in the end with his part in the goals, but Harry Winks was exceptional in midfield, constantly driving Spurs forward and keeping them positive with his use of the ball.
Son fails to shine
Although he was full of running, Son Heung-min struggled to influence the game, with Denzel Dumfries generally frustrating the South Korean. He also picked up a yellow card for a foul on Hirving Lozano and was replaced by Llorente.
Spurs return to Champions League action on November 28 when they host Inter in a vital match, following Premier League meetings with Crystal Palace and Chelsea. PSV have Eredivisie encounters with De Graafschap and Heerenveen coming up, before then facing Barcelona in Europe, a match that will likely bring their elimination.