The BBC have reported that a peak audience of 9.1 million people, and an average of 7.8 million people, tuned in across television and iPlayer.
This is despite kickoff not taking place until 2am, with torrential rain and scattered storms delaying the match in Mexico City by an hour.
It is the biggest television audience ever for a live UK broadcast between 2am and 4am.
There was also a huge audience on catch-up, with millions across the country prioritising a good night’s sleep and watching the game as-live on Monday morning.
A peak audience of 1.1 million, and average audience of 900,000, watched the full match re-run on BBC Two from 7.10am, while 5.9 million watched the highlights via the iPlayer and the BBC Sport website, app, and YouTube channel.
The BBC reported a 1,400% surge in iPlayer views for the contest, with many viewers experiencing technical issues amid the huge increase in demand.
After their 3-2 victory, the Three Lions will now take on Norway in the quarter-finals at 10pm on Saturday night on ITV.
England's win over DR Congo in the previous round, which kicked off at 5pm on Wednesday July 1, is still the highest viewed game of the World Cup so far in the UK, with a peak audience of 16.3 million.
During the group stage, England’s audiences peaked at 15.4 million against Croatia and Ghana, and at 13.76 million against Panama.
The audience for the Mexico match remained comfortably below the UK’s post-midnight record.
A peak of 18.5 million viewers tuned in for the dramatic conclusion of the 1985 World Snooker Championship final, watching Dennis Taylor take on Steve Davis.
That match, known as The Black Ball Final, saw Taylor prevail in a nail-biting final frame on the final black, with the dramatic match-winning pot taking place at 12.25am.