The male-skewed channel is to launch on November 1 with Unilever brands including Lynx body spray, Sure for Men and Marmite set to advertise.
As well as Unilever products securing the first ad on ITV's launch in 1955 with Gibbs SR toothpaste, the FMCG giant bought the first ad break for ITV3's launch night on November 1 last year.
Nigel Cowlin, Unilever's head of media and communication UK and Ireland, said: "Unilever is delighted to extend the 50-year relationship of Unilever's famous famous brands with ITV."
The deal was negotiated by MindShare on behalf of Unilever and ITV Sales.
More advertisers are keen to get in on the launch channel deals with French car manufacturer Renault booking the first ad break for Channel 4's recently launched "adult" channel More4.
ITV4's programme line-up includes the hotly anticipated remake of drama 'Kojak', live Uefa Champions League matches and cult films such as 'Carlito's Way' and 'The Fast and the Furious' to headline.
The main focus of the channel will be drama, comedy, movies and sport, appealing to its target audience of 25- to 44-year-old males.
The channel has a separate identity from the rest of the ITV family, with a distinctive logo. ITV is planning extensive off-air promotion to back the launch unlike ITV3's debut, which received a relatively soft launch with on-air promotion on ITV1 and ITV2.
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