The duo have collaborated on the upbeat pop track, which will be taken from Shakira's self-titled album.
In a photo posted to Twitter yesterday (29 January), the two popstars smoulder as they lay next to each other while smoking on cigars.
And in a preview clip of the video, which is expected to premiere tonight on VEVO (30 January), Shakira and Rihanna look fierce as they perform sultry dance moves against a wall.
Speaking in a behind-the-scenes video released this week, Shakira said: "This song combines both the reggae and the rock spirit. That's why I thought that Rihanna was perfect. She was the other half for this."
Mum-of-one Shakira, who gave birth to son Milan in January last year, also penned an open letter to fans on Facebook last week explaining that her album took two years to make.
"The work on this album has spanned a very eventful time, with many ups and downs but ultimately, the happiest period in my life thus far, including the birth of my son," she explained. "Throughout the course of creating this body of work, I learned a lot about myself.
"Though I didn't realise it at the time, all the directions I began exploring in the initial phases of recording were helping to pave a path for me of rediscovery. In the end I realised that I will always be a little bit of everything and I don't have to choose.
"Most importantly, I am enough. Imperfections and all. So what I am offering you now is just that. Nothing more. A little bit of rock, a little bit of folk, a little reggae and naturally some dance - but as always, and above all, a lot of heart."
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Watch Shakira and Rihanna in the teaser video below: