The broadcaster has signed a six-figure deal with Media-Com that will see its clients embed 30-second TV commercials into online and mobile highlights of the show.
Other advertisers due to take part in the activity over the coming weeks include GlaxoSmithKline, EA Games and Remington.
The partnership with MediaCom will allow ITV to use its website and mobile portal to make clips of I'm a Celebrity available free for the first time. It follows a similar initiative offering a limited amount of Love Island content online in July.
The broadcaster is significantly stepping up its online and mobile coverage of I'm a Celebrity. All primetime ITV1 broadcasts of the show will be streamed live via mobile, with afternoon instalments available online.
The initiative is part of a wider ITV strategy to use emerging digital platforms to offset declines in TV advertising. Revenue from the broadcaster's digital operations rose by 25% during the first half of this year; ITV1's advertising revenue dipped by 8% over the same period.
'It is becoming increasingly important for us to use digital platforms to exploit our biggest programme brands,' said Colin Ramsay, head online sales at ITV.