The service offers shows including ITV soap Coronation Street
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ITV has become the first terrestrial broadcaster to simulcast its programmes on mobile phone handsets in the UK.
Initially flagship channel ITV1 and quiz network ITV Play are being offered on the 3 network, with users charged daily or monthly rates.
Shows such as Coronation Street, The X Factor and Prime Suspect can be viewed by some 3.7 million customers via their handsets, the broadcaster said.
Highlights packages will also be made available to download on demand.
ITV's other channels are expected to be available on 3 in the coming months and will "roll out fairly quickly from now onwards", a spokeswoman for the network said.
The service would be available to nearly 90% of the UK's population, ITV claimed.
Emerging technology
Other broadcasters have shown an interest in such technology over the past year.
Sky joined with Vodafone in November to launch a 19-channel mobile service.
The BBC has also offered pre-recorded content for mobiles.
Recently this included bonus clips to accompany Rob Brydon's BBC Three comedy Annually Retentive.
An experiment by O2 last year gave some 400 people in Oxford access to 16 channels, with 80% of participants saying they would subscribe to a mobile TV service if it was available.
Separately, BT offered video from Sky News, Channel 4 and Cartoon Network amongst others, which was viewed for an average of more than an hour per week.
In May, people who watched programmes on mobile phones or computers were told they needed a TV licence to do so.
Otherwise they may face fines of £1,000 because these broadcasts are governed by the same rules as traditional television sets, TV Licensing said.