Williams will take up his new position at the end of March, reporting to James Murdoch, who became chairman and chief executive of News Corporation in Europe and Asia in December last year.
Williams will take over Daintith's duties, as well as acting as chief financial officer across News Corporation's operations in Europe and Asia, including Sky Italia, Star TV and News Corp Europe.
He will be based in London but will remain as a non-executive director on the board of Sky Italia.
Williams said: "I'm extremely excited to be taking on this new position working for James across the breadth of News Corp activities throughout Europe and Asia, ranging from operations in Eastern Europe to the already very successful UK newspaper business.
"At the same time I am very proud of the team at Sky Italia and look forward to remaining involved as a member of the Board."
Williams joined News Corporation in 1996 as chief financial officer of the Australian pay-TV operation Foxtel and in 2000 became chief financial officer for News Corporation's newspaper and other interests throughout Australia and New Zealand. He was appointed chief operating officer of Sky Italia in January 2003.
Daintith, who was appointed CFO of News International in September 2005, follows in the transatlantic footsteps of a number of News International executives moving to Dow Jones over the last few months after the completion of News Corp's acquisition of the company for $5.6bn (£2.7bn) in August last year.
First to leave News International was Les Hinton, the executive chairman, who was named as chief executive of Dow Jones in December.
Hinton was followed to New York by Robert Thomson, editor of The Times, who was appointed publisher of Dow Jones and The Wall Street Journal. Thomson was replaced as editor by James Harding, former business editor of The Times.
Ian Weston, former corporate development director of News International, then followed suit after being made senior vice-president of special projects at Dow Jones.
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