The gorgeous, Oscar-winning actress will star in 'Inhuman Traffic', which will air across MTV Networks Europe on February 10.
The 30-minute documentary will reach up to 146m households and will be streamed live through the campaign's dedicated website.
The documentary, which follows the stories of real people affected by trafficking, will also be made available free of charge and rights free to broadcasters worldwide.
'Inhuman Traffic' is the lead feature of MTV Europe's Exit campaign to stop exploitation and trafficking.
According to Jolie: "I hope that MTV's Exit campaign will empower women and girls in particular to protect themselves from trafficking by making informed decisions about their futures and help all of us to understand that we have the responsibility -- and the power -- to help end exploitation and trafficking, wherever they occur, in whatever form."
Other elements of the Exit campaign include 'Parallel Lives', a series of five short films highlighting trafficking messages that will air across MTV Networks Europe from March.
Jolie, who is also a United Nations goodwill ambassador, has starred in Hollywood films 'Tomb Raider', 'Gone in 60 Seconds', 'Alexander' and 'Girl Interrupted', for which she won an Oscar.
Her latest film, 'Mr and Mrs Smith', with Brad Pitt is about to be released. Jolie's off-screen relationship with Pitt has been picked up on by worldwide gossip magazines, speculating that the demise of Pitt and Jennifer Aniston's four-and-a-half year marriage was down to Jolie, after pictures of her and Pitt looking cosy after filming surfaced in the press.
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