Hathaway, who won an Academy Award in 2013 for her role in Les Miserables, is a long-time supporter of women's rights who will promote policies such as affordable childcare and parental leave, said Mlambo-Ngcuka.
"To make the case for how this will increase opportunities for women, we needed an advocate who had the intellect and passion to tackle this complex issue. Within moments of meeting Anne, I realised that we had found our woman," she said.
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Known for her roles in The Devil Wears Prada, Brokeback Mountain and The Dark Knight Rises, Hathaway also co-hosted the Academy Awards ceremony with actor James Franco in 2011.
She has served as an advocate for Nike Foundation, travelled to Kenya and Ethiopia to raise awareness on child marriage and narrated Girl Rising, a CNN documentary film on female education.
"I feel honoured and inspired by this opportunity to aid in advancing gender equality," the actress said in a statement.
- AAP