The Barbados-born singer's Autumn/Winter 13 range for the British retailer has the same urban feel as her debut collection, although a 'sporty chic' vibe has also been introduced.
The singer's love of tight-fitting outfits is reflected in the array of bodycon mini dress, tiny hotpants and crop tops.
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Other elements of the star's signature style comes through in oversized jumpers, beanie hats, bomber jackets and a daring thigh-high towering pair of camouflage boots with a stiletto heel.
Rihanna's co-designer Adam Selman recently spoke about working with the superstar.
"The way I approach winter style is to layer up summer clothes and Rihanna does the same," he told Vogue.
"But there are coats and sweatshirts – those pieces are key. It's a little more refined."
Rihanna unveiled her debut collection for River Island with a catwalk show during London Fashion Week back in February. It remains to be seen whether she will appear on September's schedule.
The collection will be released in two stages – autumn and winter. Autumn's offerings, set to hit the shop floors on 12 September, have a sportier feel, while the winter ware will be geared more towards the party season, as it lands in November.
The ad campaign was shot was a "New York street vibe" by photographer Lachlan Bailey. Rihanna herself was responsible for the creative direction.
Rihanna's own hairstylist, Yusef Williams, was behind the coiffed manes of models Nayasha Kusakina, Milou Van Grossen, Ji Hye Park and Tati Cotliar.
Fans in the US and Japan will once again be able to get hold of the collections exclusively at Opening Ceremony stores.