Hosted by Adrian Chiles, ITV1's full coverage averaged 12.37m (49.4%) between 7pm and 10.10pm, managing a peak of 18.5m and an audience share of around 65% as the Ukraine match reached its conclusion.
England v Ukraine beat the tournament's previous high in the UK, England v Sweden last Friday (June 15).
Over on BBC One, a repeat of Inspector George Gently mustered 2.25m (8.2%) between 8.30pm and 10pm. BBC News at Ten won its slot with 4.88m (22.5%), retaining its lead over ITV News despite the circumstances in ITV1's favour.
Big Brother anchored Channel 5's schedule with 1.34m (7.1%) at 10pm, prior to which 1.04m (3.7%) watched CSI.
Embarrassing Bodies was Channel 4's most-watched programme of the evening with 1.08m (4.1%) at 8pm (+1: 192k/0.7%).
Meanwhile, The Hairy Bikers: Mum Knows Best (1.49m/6.6%), Ocean Giants (1.21m/4.5%) and Great Ormond Street (1.39m/5%) held up well for BBC Two.
Overall, ITV1 obliterated competition in primetime with 44.7% (+1: 0.3%), far ahead of BBC One's 14.6%. BBC Two claimed third place with 5.4%, followed by Channel 5's 3.8% (+1: 0.3%) and Channel 4's 3.2% (+1: 0.6%).
BARB ratings data supplied by Attentional