The climax of England's World Cup penalty shootout win over Colombia was watched by 23.6 million viewers on ITV, according to overnight figures.
More people tuned in between 21:50-21:55 BST on Tuesday than at any other time since the 2012 Olympic closing ceremony.
A record 3.3 million people watched online via the ITV Hub, ITV said.
England's victory means they will face Sweden in the quarter-finals. That game will be shown on BBC One on Saturday.
Tuesday's match ended the so-called "curse of ITV" - which had seen England win just one World Cup match broadcast on the network over the past 20 years.
On the BBC, the team emerged victorious in nine out of 13 matches during the same time period.
However, the clash with Colombia went right to the wire.
Harry Kane gave England the lead with a penalty in the 57th minute before Colombia scored a dramatic equaliser in added time to send the match to extra time and penalties.
Eric Dier scored the decisive spot-kick to give England victory 4-3 on penalties.
An average of 20.1 million watched the last 16 match in its entirety.
ITV said it was the highest peak audience for live sport since England played Portugal in the 2004 European Championships.
According to the broadcaster's figures, the most-watched single minute of Tuesday's game was 21:52 BST, when 24.4 million people tuned in.
At this point roughly four in five people watching TV in the UK (81%) were tuned to ITV.
The knock-out match proved a bigger draw than England's group games - more than 18 million watched the matches against Tunisia and Belgium at their peaks, while 14 million saw the win over Panama.
The game also saw a record number of streams of a live event with 3.3m simulcast requests on the ITV Hub. England's opener with Tunisia was previously the most popular online match with 3.22m viewers.