The match, in which Liverpool scored two goals in the last five minutes including one from club captain Steven Gerrard, drew a 24.1% share of the audience between 7.30pm-10pm.
The match contributed to a disappointing launch night for returning BBC One drama 'Hotel Babylon'.
The first episode of the eight-part series, in which Max Beesley and Dexter Fletcher help run a five-star hotel, was watched by 5m viewers and a 24.1% share at 9pm, well below the series average of 5.8m.
Channel 4 performed well in the 9pm slot, with a 'Bodyshock' special 'The Girl with 8 Limbs' attracting a more than respectable 3m viewers and a 12% share.
Including Channel 4+1's time-shifted audience, the programme earned 3.4m viewers and 13.4% share.
Five's perennial favourite, 'CSI: Crime Scene Investigation', continues to deliver solid audiences. Last night's instalment brought 3.1m viewers and a 12.1% share at 9pm.
Five's new-look news programme, fronted by Natasha Kaplinsky, has boosted its audience in only its second outing since the former BBC newsreader made her debut on Monday.
The 5.30pm edition pulled in 1.4m viewers and a 6.1% share, up from 1m on Monday. The second edition at 7pm lured 798,000 and a 2% share, compared with 400,000 on Monday.
It is early days but Kaplinsky has more than doubled audiences for 'Five News' in only her first week. The show averaged 600,000 viewers in its former slot at 5.30pm during the last six months, while the later edition averaged 283,000 viewers in an unchanged slot at 7pm.
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