The 23-year-old Bajan-born singer, who was named the face and body of the brand's underwear and jeans collection last summer, acts out a bad dream in the moody black and white video.
She also previously posed for photographs for the campaign in her underwear, which saw her win the 'Sexiest Advert of 2011' accolade by Advertising Age.
The magazine commented: "It's Rihanna at her sexiest. She's never looked this good. She's in amazing shape and the pictures are stunning."
The star unveiled a clothing collection for the Italian fashion house last November.
Other celebrities to have modelled for the Italian fashion house include Megan Fox, David Beckham and Cristiano Ronaldo.