A pre-nuptial agreement signed before their 1999 wedding will dictate Ms Deng's claim to a share of his $11billion (pounds 7billion) wealth.
Rupert Murdoch has filed for divorce from his wife, Wendi Deng, adding personal turmoil to the most turbulent era in the billionaire media tycoon's 60-year career.
The News Corporation chairman, 82, said in a petition to New York's supreme court that their 14-year marriage, his third and her second, had "broken down irretrievably" during the past six months.
His separation from Ms Deng, 44, who acted as his gatekeeper and, on one occasion, personal bodyguard during the phone hacking scandal, caused surprise in the media industry on Thursday.
Michael Wolff, Mr Murdoch's biographer, said: "Wendi once told me that this is his reaction when things go wrong in business or his personal life. He makes a decision and it's over. He feels bad for a day and then forgets about it."
Murdoch requested that custody of the couple's daughters Grace, 11, and Chloe, nine, be shared between him and Ms Deng, a Chinese-born graduate of Yale University 38 years his junior.
A pre-nuptial agreement signed before their 1999 wedding will dictate Ms Deng's claim to a share of his $11billion (pounds 7billion) wealth.
His second wife, Anna, reportedly received a $1.7billion divorce settlement. Aides said that the divorce would have no impact on News Corp, which is controlled by a family trust. Ms Deng made global headlines in July 2011 by slapping a protester who tried to push a cream pie into Mr Murdoch's face as he testified to MPs on phone hacking.
She is renowned for her ambition across business, through News Corp and solo ventures, and the Manhattan social scene.
A former nanny to the couple, who was previously described by a spokesman for the Murdochs as a "disgruntled former employee", said last year that Ms Deng "curses Rupert all the time.
A lot of f-words. She's always yelling, crying". She added: "Everyone who works for her hates her and is scared of her." Ms Deng embarrassed her husband early in their marriage by telling an associate in Hong Kong that "Rupert takes Viagra, but he doesn't really need it".
Having grown up poor in Jiangsu, China, she moved to the US in 1988 with an American couple, Jake and Joyce Cherry, who had been working in China and sponsored her through university.
Mr Cherry left his wife for Ms Deng after an affair. They married in 1990 but divorced. Ms Deng then met Mr Murdoch while working at a News Corporation subsidiary in Hong Kong.
They married two weeks after Mr Murdoch divorced Anna, his wife since 1967 and the mother of Lachlan, Elisabeth and James. He was married to Patricia Booker, the mother of his eldest daughter Prudence, for 11 years from 1956.
Recent reports have claimed that Ms Deng had "immersed herself" in a circle including Tony Blair, Nicole Kidman and Bono, and that Mr Murdoch was rarely present. Tensions are also believed to have mounted between Ms Deng and Mr Murdoch's older children, who were said by one News Corp executive only to "do their best to be courteous" around her.
"The backdrop is that Rupert is having to deal with a lot of things in his life right now," said Mr Wolff. Mr Murdoch is currently overseeing the splitting of News Corp in two. A spokesman for Mr Murdoch declined to comment on why the relationship had broken down, whether any third party was involved or whether Ms Deng would contest the petition.
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