Roy Hodgson's England lost 4-2 on penalties after the game finished 0-0, following 90 minutes and extra time. The audience figures peaked at over 23 million (77% share) for the spot kicks, which ended in heartbreak for English fans after Ashley Young and Ashley Cole fluffed their chances.
The game averaged 20.3 million (68% share) viewers between its 7.45pm kick-off and the end of the shoot-out at 10.20pm. The whole coverage of the event including punditry from the Gary Lineker-anchored BBC team averaged 17.4 million (62 %).
TV critic Ian Hyland joked on Twitter about the huge ratings: "23m watched England go out on penalties last night. That's one of the highest ever TV audiences for a repeat."
Ratings were increased considerably from the first-round matches with Ukraine, France and Sweden, which reached averages of 16.1 million, 12.3 million and 14.1 million viewers respectively.
Last night's viewing figures topped last year's royal wedding of Prince William and Kate Middleton, which peaked at 19.27 million for BBC. However, the royal occasion was watched by a higher number (26.1m - 92.4%) across all channels.
England's defeats means that the semi-finals on Wednesday (June 27) and Thursday (June 28) will now feature Spain v Portugal and Germany v Italy.