Kane had gone three games without troubling the scorers at the Tottenham Hotspur Stadium but he put that right with two goals in four minutes to seal the three points in what was a curious early evening in north London.
Spurs looked like starting the new Premier League campaign with a defeat after John McGinn's early opener gave Villa a dream start to life back in the big time.
Tanguy Ndombele showed just why Tottenham broke their transfer record to bring him to the club with a fine leveller 17 minutes from time before Kane stole the headlines with two clinical finishes that masked a match that provided more questions than answers.
Although Kane and Ndombele were the goalscorers it was the introduction off the bench of Christian Eriksen that turned the game, with Mauricio Pochettino choosing not to start the Denmark midfielder as his future at the club remains uncertain.
Spurs stalwart Jan Vertonghen was also not included in the matchday squad at all and suddenly his future looks in doubt as he is in the final year of his contract.
There might have been some sort of post-mortem for Spurs had they not turned things around, having initially struggled to respond after falling behind.
Lucas Moura should have put Spurs ahead inside the opening five minutes, but he planted a free header at goalkeeper Tom Heaton from Danny Rose's pinpoint cross.
Spurs would have fancied asserting their authority with an early goal, but instead they were picking the ball out of their own net as they were undone by route one in the ninth minute.
Tyrone Mings' long punt caused mayhem and McGinn burst through the acres of space in the Spurs defence and slotted home to give his side the lead.
For all the optimism that the new season brought for Spurs and with Ndombele in the starting line-up, there was something all-too familiar about their play.
They laboured in a way that they did towards the end of last season, having plenty of the ball but lacking a cutting edge.
And they could have found themselves further behind but Trezeguet could not get enough on his shot and Hugo Lloris held with ease.
Spurs began to pick their way through the Villa defence as half-time neared and Kane had two chances, the first he headed over from Ndombele's cross and the second he rolled wide of the post after being put through one-on-one, though that would have needed a VAR check as the offside flag went up.
The start of the second half was much more promising for the hosts as they put Villa under immediate pressure and forged a great chance in the 50th minute.
The ball fell to Moussa Sissoko at the far post, but for all his strengths he is a player that tends to freeze as soon as he gets into the opposition penalty area and his shot from eight yards out went for a throw-in.
Spurs had to resort to bringing Eriksen off the bench and his introduction changed the game.
He began opening Villa up and was involved in Spurs' equaliser as his corner was not cleared properly and Ndombele found the bottom corner from the edge of the area in fine style.
Spurs threw everything at their visitors, who needed Heaton to keep out Eriksen's free-kick, and they eventually got their reward in the 86th minute.
Erik Lamela won the ball back and played in Kane, with the help of a deflection, and the England captain made no mistake from eight yards.
The game was settled in the 90th minute as Kane got his second with a trademark finish from inside the area.