Graf, will relinquish his current duties as chairman of the Press Standards Board of Finance, the body that funds the Press Complaints Commission, and chairman of the Broadband Stakeholder Group when he takes up his role at Ofcom on January 1 2006.
He replaces outgoing deputy chairman Richard Hooper, who held the post for three years.
Graf began his career in journalism in 1983 at the Liverpool Daily Post & Echo and was appointed chief executive of Trinity International Holdings in 1993.
He became chief executive of Trinity Mirror Group when the company merged with the Mirror Group in 1999, a position he held until September 2002.
In 2003, Tessa Jowell, the secretary of state for media, culture and sport, commissioned Graf to conduct an independent review of BBC Online.
The report was delivered in May 2004 and formed the basis of the corporation's online strategy leading up to Charter Renewal.
In his new role, Graf will chair the Ofcom content board, a committee of the main Ofcom board with responsibility for the regulation of television and radio.
He will also be a member of the Ofcom Remuneration, Audit and Nominations Committees.
David Currie, Ofcom chairman, said: "Philip's appointment further strengthens the sector experience and expertise around the Ofcom board."
In addition, Sean Williams, an Ofcom partner with responsibility for competition and investigations since 2003, has been promoted to executive director, and Polly Weitzman, Ofcom's director of competition law, has been promoted to the newly created post of general counsel.
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