A 98-second brace from Jude Bellingham handed the Three Lions a quick-fire 2-0 first-half lead against the run of play.
However, they almost immediately saw their deficit halved when Julian Quinones smashed home for Mexico three minutes before the break.
Again, though, Mexico responded quickly, scoring a penalty of their own through Raul Jimenez after a challenge by Kane.
Here, Standard Sport picks out 10 key moments that contributed to one of England’s greatest World Cup nights…
Rice yellow sets tone for chaotic game
A lot had been made about how England were going to cope against the backdrop of a passionate home crowd at the Azteca.
So, when Declan Rice was booked inside the first minute, it set the tone for how the game was going to play out, with Mexico contesting every challenge to referee Alireza Faghani.
In the main, England kept their cool, but they still ended up a man down and with four yellow cards as they sought to drag Mexico into a physical game.
Pickford defies critics to make important early save
By his own exacting standards, Jordan Pickford has endured a difficult start to England’s World Cup campaign.
Widely deemed to be at fault for DR Congo’s goal during England’s nervy round-of-32 comeback victory, Pickford produced a timely reminder of his qualities early on against Mexico as he saved expertly from Jimenez’s low header.
It would be the first of a number of fine stops in a superb performance from England’s No1.
Rising to the occasion: Jude Bellingham heads in the opening goal for England against Mexico
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Bellingham nets twice in quick succession
Cometh the hour, cometh the man. Bellingham has always been one for the big occasion, and he showed up again to puncture a febrile atmosphere towards the end of the first half.
By design, England had sat in and suffered for much of the opening 45 minutes, but they sprang free in style to stun Mexico as Bellingham headed home from Bukayo Saka’s cross before turning in from close range just over a minute later after Kane had squared the ball across the six-yard box.
Mexico get an instant reply
If Bellingham has been England’s talismanic figure for much of this tournament, then Quinones has come to define Mexico’s free-willed and aggressive style under manager Javier Aguirre.
Known for his power and directness, Quinones became the joint-highest Mexican goalscorer in a single World Cup campaign as he smashed past Pickford on the half-volley to give Mexico a foothold three minutes before the break.
Had Mexico been sharper in front of goal, they probably would have capitalised on the momentum generated from Quinones’ fourth goal of the tournament.
Reducing the deficit: Julian Quinones scores again for Mexico, who couldn’t then capitalise
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Bellingham makes another timely intervention
After Quinones had got Mexico back into the game, the atmosphere inside the Azteca turned as they hunted for an equaliser before the break.
The hosts were causing all sorts of issues with their crosses, and Bellingham in particular was guilty of failing to track his man, as seen for Quinones’ goal.
Bellingham was nearly culpable again for losing his man as Mexico swung in another cross before half-time, but the England midfielder recovered superbly to hook the ball clear for a corner as Carlos Montes threatened to score from close range.
Quansah sees red after VAR review
Despite the referee initially playing on after Quansah had made a sliding tackle, he was recommended to take another look after the Mexico bench reacted angrily to the force with which he had made contact – leading to chaotic scenes on the touchline.
Quansah’s dismissal gave England an uphill battle, but one they managed superbly as they held on for a remarkable victory.
Seeing red: Jarell Quansah becomes just the fourth England player ever to be sent off at the World Cup
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Kane and Jimenez trade penalties
After Quansah’s red card, England were given an almost immediate reprieve after they were awarded a penalty on the hour mark when Gordon was brought down by Mexico goalkeeper Raul Rangel.
Kane dispatched his penalty calmly to restore England’s two-goal lead, but soon gave away a penalty at the other end having been adjudged to have kicked Brian Gutierrez’s foot in the area.
After a VAR review, a penalty was awarded, which Jimenez scored to bring Mexico back to within a goal and ramp up the pressure inside the Azteca with a little over 20 minutes to play.
Tuchel’s subs make the difference again
Thomas Tuchel has utilised his bench to great effect so far at this tournament, and Sunday night was no different.
With England down to 10 men and holding on against wave after wave of Mexico attacks, Tuchel looked to change things in defence.
Mexico’s crosses had been causing all sorts of danger, so Tuchel brought on Dan Burn and Djed Spence to try to cut them out at source.
It was a move that worked well as Mexico struggled for clear-cut chances despite having the man advantage.
Spence makes last-ditch challenge to deny Gimenez
Spence faced plenty of criticism, a great deal of it unfounded, for his performance against DR Congo.
It meant the Tottenham full-back, who has been carrying a minor injury at this World Cup, started on the bench against Mexico as Tuchel opted to bring Quansah back into the fold after his return from an ankle problem.
Introduced as a second-half substitute, Spence did not appear to be hung up on the fact that he had been dropped to the bench, and he made a crucial tackle to prevent Santiago Gimenez from breaking into the area.
Standing tall: Dan Burn blocks an attempted bicycle kick from Raul Jimenez in the dying moments
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Towering Burn shuts door on Mexico comeback
By the end, England had dropped into a deep low block and were defending for their lives as they tried to see out 11 minutes of additional time at the end of the second half.
Burn was at the centre of everything England did defensively in the final throes of the game, and after he made a heroic late block from Jimenez’s bicycle kick, some of Mexico’s players turned to the skies to curse their luck.
In truth, there was nothing lucky about the way England frustrated Mexico, and Burn’s involvement off the bench was no happy accident.
