Coverage of the quarter-final between England and Italy averaged 17.37m (62.3%) for BBC One between 7pm and 10.45pm, peaking with 23.2m (77.4%) for the penalty shoot-out.
Interest in the football affected the other terrestrial channels, as Channel 5's Once Upon a Time (776k/2.5%) and Big Brother (775k/2.5%) both sunk to all-time lows.
Emmerdale was ITV1's best-rated programme with 4.56m (21.3%) at 7pm (+1: 186k/0.6%), then 2.14m (8.5%) stuck around for You've Been Framed.
A Touch of Frost repeat took 1.96m (6.5%) between 8pm and 10pm, adding 151k (0.5%) on timeshift.
Channel 4's One Born Every Minute entertained 518k (1.7%) in the 8pm hour, after which The Secret Millionaire nabbed 670k (2.2%) and 159k (0.6%) on +1.
Over on BBC Two, Oceans (1.4m/5.9%) and Secrets of Our Living Planet (1.36m/4.5%) secured respectable audiences.
Overall, BBC One obliterated ITV1 in primetime with a colossal 61.3% share versus 7.2% (+1: 0.5%). BBC Two earned third place with 4.3%, followed by Channel 4's 2.7% (+1: 0.6%), and Channel 5's 2.2% (+1: 0.2%).
Mark Wright's Hollywood Nights continued with 312k (1.3%) on ITV2 at 10pm, adding 148k (1.3%) an hour later.
BARB ratings data supplied by Attentional