Marc Webber, who takes the role of head of content at ITV.com, was responsible for introducing video to the Sun's online operation and worked on the MySun community offering launch.
Webber will have overall control for managing content across ITV.com's main genres of news, gossip, soaps, dramas, kids, sport and entertainment.
He has been charged with working alongside ITV Network Centre programme controllers to grow the popularity of the website, which had a £20m relaunch last year.
ITV has also hired Kate Bradshaw, director of new media production at IMG, as head of online external commissioning.
Both Webber and Bradshaw, who in previous roles has developed a broadband on-demand channel for BBC2 and launched UKTV's website, will report in to the ITV Broadband managing director, Annelies van den Belt.
"Marc brings with him an ideal blend of traditional broadcast experience and in-depth knowledge of the demands of online content, while Kate has an intuitive understanding of internet behaviour with a proven track record of devising and implementing successful commercial applications," she Van den Belt.
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