A previous collaboration by the pair reached number
two in 2010
Rihanna has joined The Beatles and Elvis Presley as one of just three acts to top the UK singles chart seven times over seven years.
The singer has stormed into the number one spot, as the featured artist on rap star Eminem's new track The Monster.
The pair held off a challenge from boyband One Direction, who were tipped to have their fourth number one with Story Of My Life.
The Monster is Eminem's first number one hit since 2006.
A previous collaboration with Rihanna, Love the Way You Lie, made it to number two in the UK charts in 2010.
The track is taken from his latest album Marshall Mathers LP 2, which also features this month's top 10 hits Berzerk and Rap God. It will be released on 5 November.
New Zealand singer Lorde, whose track Royals debuted at number one last week, fell one place to number two.
Fat Boy Slim's Eat Sleep Rave Repeat entered the chart at number three, giving the DJ his first top 10 hit in 12 years.
Former number one Counting Stars, by OneRepublic, rounds off the top five.
In the albums chart, Arcade Fire's fourth album Reflektor knocked Katy Perry's Prism off the top spot, outselling the US singer by nearly two to one over the past week, according to the Official Charts Company.
James Blunt's Moon Landing is at three, while Lorde's album Pure Heroine debuts at four.
James Blake enjoyed the fruits of his Mercury Prize success, with his album Overgrown soaring up the charts to number 23, having been previously outside the top 200.
There was also a re-entry into the top 40 for Lou Reed's album Transformer following the singer's death last weekend.