The TV audience peaked at 15.6 million just before half-time.
The entire broadcast attracted an average audience of 11.5 million, making it one of the most watched programmes of the year so far.
The viewers saw England go down to a 2-1 defeat to Italy in the countries' first Group D match in Manaus, Brazil.
The game kicked off at 23:00 BST (22:00 GMT) and more than 13 million people stayed up until the final whistle just before 01:00 BST, the overnight figures showed.
In comparison, the audience for England's first match at the 2010 World Cup against the USA peaked at 20.1 million, with an average of 16.1 million - but that game kicked off at 19:30 BST (18:30 GMT).
The opening match of this year's tournament, in which Brazil beat Croatia, was watched by a peak of 12.6 million people on ITV.
The following night, the Netherlands' 5-1 defeat of Spain hit a peak of 11.4 million on BBC One.
The biggest peak TV audience of the past 12 months came when 17.3 million watched Andy Murray win Wimbledon last summer.
The TV ratings only count people watching at home. Before the England match, the British Beer and Pub Association estimated that three million people would watch in pubs and bars.
Thousands more saw the match on big screens at the Isle of Wight music festival, where fans had to choose between watching the football and watching the Red Hot Chili Peppers on the main stage.
Meanwhile, Twitter said 7.2 million tweets were sent worldwide during the England and Italy game.