He will report to Robin Pembrooke, managing director of ITV Online and On Demand, and Peter Fincham, ITV director of television.
Williams will be "responsible for implementing a strong collaborative approach to commissioning ITV digital content across platforms as part of the wider transformation strategy," according to the broadcaster, and will "play a key role in shaping ITV's digital consumer proposition in order to increase audience engagement."
Pembrooke said: "Appointing Richard is a key step for us in the transformation of our online and on-demand offerings and his role will be vital in making sure cross-platform thinking is at the heart of the ITV commissioning process.
"He brings with him a wealth of experience in online commissioning and production and I look forward to welcoming him as a central member of both mine and Peter's teams."
Williams joins from BBC Vision, the broadcast and production group, where he is head of multi-platform production and production modernisation.
Prior to that, he held several digital roles including creative director of multiplatform productions at BBC Vision and executive editor for factual.
Fincham said: "While ITV's programming is attracting record television audiences, our viewers are also consuming our content across a range of different platforms.
"I'm delighted that Richard will be working closely with the commissioning team to extend the reach of our programme brands in the digital world."
On Monday, ITV launched the first episode of an online about 'Coronartion Street' couple the Barlows, called 'Ken and Deidre's Bedtime Stories'.
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