The programme, which was organised by Robbie Williams and featured an England team of celebrities and sportsmen taking on a Rest-Of-The-World side, averaged 5.21m (23.7%) for ITV1 between 6pm and 10.15pm.
On Sky1, a double-bill finale of espionage drama 24 attracted respective audiences of 616k (2.5%) and 596k (3.1%) from 9pm.
BBC One's coverage of the BAFTA Television Awards 2010 was watched by 4.14m (17.1%) between 8pm and 10pm.
Earlier on the channel, Halcyon River Diaries brought in 3.62m (20.2%) in the 7pm hour, followed by Countryfile with 5.07m (23.6%).
A repeat of Top Gear averaged 1.6m (6.8%) for BBC Two in the 8pm hour, and An African Journey With Jonathan Dimbleby secured 1.42m (5.7%) from 9pm.
Documentary Cameron's Black Tory took 470k (2.2%) for Channel 4 from 7pm and 67k (0.3%) on timeshift. It was followed by a screening of One Fine Day, which was watched by 1.29m (5.3%) and 113k (0.5%) on timeshift.
In the 10pm hour, Big Brother Exposed: The Inside Story appealed to 1.01m (5.3%) for Channel 4 and 129k (1.3%) on timeshift.
A screening of Robin Hood: Prince Of Thieves took 1.91m (8.2%) for Five between 8pm and 10.45pm.
Overall, ITV1 gained victory in primetime with 22.6% against BBC One's 19%. Five came in third with 7.3%, followed by BBC Two with 6.1% and Channel 4 with 4.5% (+1: 0.4%).
Elsewhere, back-to-back editions of Midsomer Murders secured respective audiences of 676k (3.4%) and 1.25m (5.2%) for ITV3 from 6pm.
On ITV2, a repeat of Saturday's final of Britain's Got Talent pulled in 495k (2.3%) from 6.30pm and 87k (0.4%) on timeshift. It was followed by the programme's results show, which averaged 167k (0.7%) and 66k (0.4%) on timeshift.
BARB ratings data supplied by Attentional