A peak audience of 23.2 million watched the England football team get knocked out of the Euro 2012 tournament.
Figures for Sunday night's match on BBC One peaked during the five minutes containing the penalty shoot-out, attracting a 77% share of the audience.
England's defeat by Italy was the most watched event on TV so far this year and had the highest peak viewing figure for any channel in eight years.
The previous peak came when England lost to Portugal in Euro 2004.
An average of 17.4 million watched the BBC's coverage of the match in Kiev, which was settled by a penalty shoot-out at 10:20 BST after it ended 0-0 after extra time.
England's previous match in Euro 2012, a 1-0 victory over Ukraine last week, was watched by an average of 16.1 million.
The 23.2 million peak audience beat the 19.9 million peak achieved by last year's Royal Wedding coverage on the BBC.
However, more people overall saw that event in April 2011 as it was also shown by other UK broadcasters.