A peak audience of 26.5 million people watched England go out of the World Cup on ITV, according to overnight figures.
That made it the most-watched five minutes of British TV since the 2012 Olympic opening ceremony.
Wednesday's audience peaked between 21:30-21:35 BST as England tried to find an equaliser at the end of extra time in the semi-final against Croatia.
But they couldn't score, meaning Croatia won 2-1 to take them into Sunday's final against France.
The overall TV match average for the semi-final was 24.3 million, which doesn't take into account people watching in pubs or on outdoor big screens.
ITV said there were also a record 4.3 million requests to watch it online on ITV Hub.
About 80% of all viewers watching TV in the UK at the time were tuned into the game.
Its ratings reflected the huge interest in England's first World Cup semi-final since 1990.
However not everyone could stand the tension and some changed channels.
The previous highest audience during this World Cup was 23.6 million for the climax of England's penalty shootout win over Colombia in the last 16.