Spurs, however, reversed fortunes dramatically at the start of the second half with two quick goals from William Gallas and Jermain Defoe.
It was a situation that called for Chelsea to show the substance to match the style this reshaped side is offering up this season. They delivered both to secure a hugely impressive win.
The outstanding Juan Mata struck twice in three minutes as Chelsea regained the ascendancy and substitute Daniel Sturridge's simple fourth in stoppage time completed a hugely satisfying performance from the Champions League holders.
Spurs were forced into a late change when Gareth Bale dropped out of their starting line-up after his partner went into labour - and it was understandable that they should miss a player of his influence.
Nothing, however, can diminish the growing sense that even though this Chelsea team is undergoing something of a transition, they have the quality to be very serious contenders for the title this season.
And, in Mata, they have a player of the highest quality as a creator and scorer who was able to cast his spell over this wonderful game.
Gallas, who endured a miserable day defensively, wasted a perfect opportunity to give Spurs the lead after only three minutes when he failed to make firm contact with Gylfi Sigurdsson's free-kick from six yards.
Juan Mata's brace was his first Premier League double and first in any competition since April 2011, when he scored twice in Valencia's 5-0 home win against Villarreal
Chelsea's approach and change in personnel allows them a great deal of fluidity. Young Brazilian Oscar is central to this change in emphasis and he showed his threat with a long-range effort that flew just wide.
Villas-Boas demonstrated his faith in 41-year-old Brad Friedel by reinstating him ahead of France goalkeeper Hugo Lloris but the veteran was powerless to stop Cahill putting Chelsea ahead after 17 minutes.
Gallas's headed clearance from Eden Hazard's corner was met by Cahill, who showed perfect technique to send a thunderous volley high past Friedel.
Spurs produced a spirited response, with Cech scrambling to save from Defoe, but Chelsea remained dangerous and Mata should have done better than shoot off target after his first effort had been blocked by Friedel.
Villas-Boas clearly demanded greater urgency from his players during the break - and he received it as they struck twice in the opening stages of the second period to turn the game around.
Villas-Boas credits 'brilliant' Chelsea
Gallas scored his first goal for Spurs when he glanced in after Jan Vertonghen hooked back from the far post then Defoe added the second after 54 minutes, turning in Aaron Lennon's driven cross for his 200th career goal.
It was time for Chelsea to demonstrate their own resilience and they did not disappoint, producing two quick goals from Mata to regain the advantage Spurs had taken from them.
Another poor clearance from Gallas offered Mata the opportunity to shoot low past Friedel from the edge of the area, then the Spaniard accepted Eden Hazard's pass to send a composed finish past Friedel.
Villas-Boas introduced Emmanuel Adebayor for the subdued Clint Dempsey in an attempt to regain the initiative - but it was fitting that Mata should have a say in the final act as he rolled a perfect cross in for Sturridge to score with ease.
Full Time The final whistle is blown by the referee.
The referee blows for offside against Jermain Defoe. Free kick taken by Petr Cech.
Raniere Sandro takes a shot. Gary Cahill gets a block in.
Header from deep inside the penalty area by Emmanuel Adebayor goes harmlessly over the crossbar.
The assist for the goal came from Juan Mata.
90:00 +0:08 Goal scored
Goal - Daniel Sturridge - Tottenham 2 - 4 Chelsea Daniel Sturridge scores a goal from close in to the bottom right corner of the goal. Tottenham 2-4 Chelsea.
Corner taken by Gylfi Sigurdsson from the right by-line.
Substitution Frank Lampard is brought on as a substitute for Eden Hazard.
Kyle Walker takes a shot. Save made by Petr Cech.
Raniere Sandro has an effort at goal from outside the area missing to the wide right of the target.
Shot from outside the penalty box by Emmanuel Adebayor goes wide right of the goal.
Fernando Torres produces a left-footed shot from close range which goes wide of the right-hand upright.
Free kick awarded for an unfair challenge on Eden Hazard by Emmanuel Adebayor. Direct free kick taken by Ashley Cole.
Aaron Lennon takes a shot. Petr Cech makes a save.
The official flags Daniel Sturridge offside. Steven Caulker restarts play with the free kick.
Free kick awarded for a foul by Emmanuel Adebayor on Mikel. Free kick taken by Gary Cahill.
Substitution Daniel Sturridge on for Emboaba Oscar.
Unfair challenge on Jermain Defoe by Mikel results in a free kick. Strike comes in from Gylfi Sigurdsson from the free kick.
Free kick awarded for a foul by Gylfi Sigurdsson on Mikel. Emboaba Oscar takes the direct free kick.
Jermain Defoe takes a shot. Blocked by Emboaba Oscar.
Emmanuel Adebayor takes a shot. Save by Petr Cech.
Shot from deep inside the area by Gylfi Sigurdsson goes over the bar.
Emboaba Oscar takes a shot. Save made by Brad Friedel.
Substitution (Tottenham) makes a substitution, with Emmanuel Adebayor coming on for Clint Dempsey.
Juan Mata takes a shot from 6 yards. Save by Brad Friedel.
The assist for the goal came from Eden Hazard.
68:47 Goal scored
Goal - Juan Mata - Tottenham 2 - 3 Chelsea Juan Mata fires in a goal from inside the penalty area to the bottom left corner of the goal. Tottenham 2-3 Chelsea.
Jermain Defoe takes a shot. Petr Cech makes a save. Outswinging corner taken right-footed by Gylfi Sigurdsson from the right by-line.
Substitution (Tottenham) makes a substitution, with Jake Livermore coming on for Tom Huddlestone.
Assist on the goal came from Emboaba Oscar.
65:49 Goal scored
Goal - Juan Mata - Tottenham 2 - 2 Chelsea Juan Mata scores a goal from the edge of the penalty area to the bottom right corner of the goal. Tottenham 2-2 Chelsea.
Unfair challenge on Clint Dempsey by Eden Hazard results in a free kick. Kyle Walker takes the free kick.
Raniere Sandro takes a shot. Comfortable save by Petr Cech.
The ball is crossed by Eden Hazard, Brad Friedel makes a comfortable save.
Eden Hazard is caught offside. Brad Friedel restarts play with the free kick.
Headed effort from deep inside the area by Branislav Ivanovic misses to the right of the goal.
Handball by Jermain Defoe. Free kick taken by Juan Mata.
Eden Hazard takes the inswinging corner, Kyle Walker makes a clearance.
Assist on the goal came from Aaron Lennon.
53:53 Goal scored
Goal - Jermain Defoe - Tottenham 2 - 1 Chelsea Jermain Defoe finds the net with a goal from inside the penalty area to the bottom right corner of the goal. Tottenham 2-1 Chelsea.
Shot by Jan Vertonghen. Save made by Petr Cech.
The assistant referee signals for offside against Eden Hazard. William Gallas takes the free kick.
Eden Hazard fouled by Kyle Walker, the ref awards a free kick. Direct free kick taken by Ashley Cole.
Gylfi Sigurdsson takes a shot. Save by Petr Cech.
Gylfi Sigurdsson takes a shot. Branislav Ivanovic gets a block in. Outswinging corner taken right-footed by Tom Huddlestone, free kick awarded for an unfair challenge on David Luiz by Steven Caulker. Petr Cech takes the free kick.
Unfair challenge on Steven Caulker by Mikel results in a free kick. Direct free kick taken by Tom Huddlestone.
The assist for the goal came from Jan Vertonghen.
46:03 Goal scored
Goal - William Gallas - Tottenham 1 - 1 Chelsea William Gallas finds the net with a headed goal from inside the six-yard box. Tottenham 1-1 Chelsea.
Free kick awarded for an unfair challenge on Clint Dempsey by David Luiz. Tom Huddlestone crosses the ball in from the free kick.
The game restarts for the second half.
45:00 +3:48 Half time
Half Time The ref blows to signal half-time.
Free kick taken by Kyle Walker.
45:00 +2:59 Booking
Booking Nascimento Ramires is shown a yellow card for unsporting behaviour.
Free kick awarded for a foul by Nascimento Ramires on Aaron Lennon.
Free kick taken by David Luiz.
45:00 +1:18 Booking
Booking Kyle Walker receives a caution for unsporting behaviour.
Nascimento Ramires fouled by Kyle Walker, the ref awards a free kick.
Jermain Defoe takes the chance to get an effort at goal. Clearance made by Ashley Cole.
Clint Dempsey takes a shot. Blocked by Gary Cahill. Tom Huddlestone takes the outswinging corner, Clint Dempsey takes a shot. Blocked by Nascimento Ramires.
The ball is sent over by Clint Dempsey, save made by Petr Cech.
Free kick taken by David Luiz.
Booking Booking for William Gallas for unsporting behaviour.
Fernando Torres fouled by William Gallas, the ref awards a free kick.
Juan Mata takes a shot from 18 yards. Save made by Brad Friedel. Shot from deep inside the area by Juan Mata clears the bar.
Clearance by Steven Caulker.
Booking Tom Huddlestone is cautioned.
Corner taken by Eden Hazard from the left by-line played to the near post,
Corner taken by Gylfi Sigurdsson from the right by-line to the near post, Emboaba Oscar makes a clearance.
The offside flag is raised against Juan Mata. Brad Friedel restarts play with the free kick.
Effort on goal by Gylfi Sigurdsson from inside the penalty box misses to the right of the target.
Kyle Walker fouled by Mikel, the ref awards a free kick. Shot on goal comes in from Tom Huddlestone from the free kick, Emboaba Oscar gets a block in.
Free kick awarded for an unfair challenge on Clint Dempsey by Mikel. Jan Vertonghen takes the free kick.
Direct free kick taken by Jan Vertonghen.
Booking Branislav Ivanovic is cautioned by the ref for unsporting behaviour.
A cross is delivered by Fernando Torres, clearance made by William Gallas.
Jermain Defoe takes a shot. Save by Petr Cech. Outswinging corner taken by Gylfi Sigurdsson from the right by-line played to the near post, Emboaba Oscar manages to make a clearance.
Eden Hazard provided the assist for the goal.
16:59 Goal scored
Goal - Gary Cahill - Tottenham 0 - 1 Chelsea Gary Cahill scores a goal from the edge of the area high into the middle of the goal. Tottenham 0-1 Chelsea.
A cross is delivered by Juan Mata, William Gallas makes a clearance. Inswinging corner taken from the left by-line by Eden Hazard, clearance by William Gallas.
The ball is sent over by Kyle Walker.
The referee blows for offside. William Gallas restarts play with the free kick.
Effort by Raniere Sandro from a long way out goes over the crossbar.
Corner taken right-footed by Gylfi Sigurdsson from the right by-line, clearance by Branislav Ivanovic.
Emboaba Oscar has an effort at goal from outside the penalty area missing to the wide left of the goal.
Inswinging corner taken by Eden Hazard, clearance made by William Gallas.
Foul by Mikel on Clint Dempsey, free kick awarded. Gylfi Sigurdsson delivers the ball from the free kick right-footed from left channel.
The game begins.
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