Portman, 29, was announced by Christian Dior Parfums to have signed up for the deal back in June, but details of her role remained a secret until December 9, the Telegraph reported.
The actress, who has never lent her face to a cosmetics or fragrance campaign until now, emerged from a transparent screen of roses in front of gathered journalists to mark her 'poster girl' debut for Christian Dior.
WWD reported that Parfums Christian Dior chief Claude Martinez called Portman "charismatic and elegant".
She joins fellow Dior 'pin-ups' Charlize Theron, who appears bathed in gold for the 'J'adore' Dior perfume, and Sharon Stone, who fronts the skincare campaign.
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