The rapper will appear on the title track for the Bajan's star's sixth studio record Talk That Talk, which will be released on November 21.
Over the weekend, Rihanna posted on Twitter: "#TTT one feature on the album! And we got the best!!!!! (sic)"
She added: "aaahhhhhhhh!!!!!!!! i wanna tell u SO MUCH about #TTT"
Although the 23-year-old did not reveal who the feature is, producer Stargate told Norwegian radio on Monday (November 7) that it is Jay-Z.
"This is the first time we do a song with Jay-Z and Rihanna together. Actually it's the first time Jay does anything on our beats," he explained to 730.no. "It was about time."
The mixer continued: "'Talk That Talk' is a mid-tempo banger with hard drums, dirty synths, and Rihanna and Jay at their best.
"We are very happy with the song and Jay's verse is crazy - same with Rihanna's part."
Calvin Harris is the second of two features on Talk That Talk, appearing on lead single 'We Found Love', which has topped charts worldwide since its release last month.
Rihanna recently revealed that the standard edition of Talk That Talk will contain 11 new tracks, while the deluxe version will feature 14 songs.
> Rihanna's 'Talk That Talk' contains four chart smashes, says producer
> Rihanna: 'New Talk That Talk album cover is ugly' - video
Watch the music video for Rihanna and Calvin Harris's 'We Found Love' below: