Graf, who was formerly chief executive of Trinity Mirror, spearheaded a report last year into how the BBC's online activities affected regional press, prompting a number of changes.
Graf is currently chairman of the Press Standards Board of Finance, the body that funds the Press Complaints Commission, and chairman of the Broadband Stakeholder Group, an advisory group to government, but will resign these positions before taking up his new post.
The three to five-year appointment was made jointly by Alan Johnson, secretary of state for trade and industry, and Tessa Jowell, secretary of state for culture, media and sport.
Graf will also chair the Ofcom Content Board, which has responsibility for the regulation of television and radio quality and standards, and sit on the Ofcom Remuneration, Audit and Nominations Committees.
Ofcom chairman David Currie said: "Philip's appointment further strengthens the sector experience and expertise around the Ofcom Board.
"I would also like to pay tribute to our outgoing deputy chairman, Richard Hooper, for his outstanding work and support over the last three years."
Graf's appointment is effective from 1 January 2006. He will draw a £100,515 annual salary for up to three days a week.
Separately, Ofcom announced that Sean Williams, partner in the Competition Group, would join the board as an executive director, and lawyer Polly Weitzman would join in the new position of general counsel.
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