The app, made by Shazam, could provide millions of viewers with direct links to websites, adverts and extra facts about products.
A growing number of TV viewers are already using phones and tablets as “second screens”, either to do other things while also watching television or to find out more about what they’re watching. Many more also talk about what television via social networks such as Twitter and Facebook.
ITV has signed the deal with Shazam to use the technology on selected commercials, and is expected to encourage viewers to provide more information online in exchange for offers.
The app, which allows users to identify music being played around them, will let viewers interact with the special adverts to enter competitions, download music and get further information about products.
It is already used in the United States, with more than half of the adverts in this year's Super Bowl being tied to the format. A version of the app is already available in the UK and is able to identify music using a phone's microphone. Currently it does not however link directly to adverts, instead displaying the lyrics in time to the songs.
Group commercial sales director at ITV Simon Daglish said: "Shazam's audio-recognition technology is at the forefront of the second screen movement which is transforming the way consumers interact with content including advertising.
"This exclusive partnership means that ITV is able to offer customers a real first for UK media and allow brands to connect directly with audiences on a large scale."