The Old Sorting Office in central London was home to the event, which was one of the hottest tickets of LFW.
Luckily, the collection didn't disappoint, with a selection of 90s-inspired pieces in bold, primary colours, including jersey maxi dresses with thigh-high splits, crop tops, bomber jackets and sheer shirts.
Also featuring predominantly in the line was tie-die, which gave a grungy look to a sleeveless jumpsuit, A-line mini-skirt, off-the-shoulder crop top and a hooded shirt dress.
Scandalous mesh vest tops and below-the-knee skirts gave the collection a gothic-tinge, while shirts tied around the waist worn over a variety of skirts and shorts harked back to early 90s grunge.
The pieces were accessorised by backwards baseball caps, oversized gold hoop earrings, headscarves, chunky biker boots and simple black heels.
The modern looks were finished off with straight cascading hairstyles, either slicked back behind the models ears or tied back. A dramatic red lip complimented the various ensembles perfectly.
Speaking backstage after the show, Rihanna said of the collection: "The girl that would wear this is full of personality, full of sass, but just loves fashion - most of all, they love fashion.
"They want to express themselves through what they wear and that's what I like to do."
The 120 piece collection goes on sale on March 5 at selected River Island stores and online with prices starting at €25.
Take a look at some photos of the Rihanna for River Island launch below.
Watch Rihanna talk about designing the collection here.
You can watch a video of the LFW show here.
An elegant jersey dress with a thigh-high split
Rihanna and her stylist Mel Ottenberg
Rihanna chose a black jersey mini-dress for the show
Block colours and simple shapes dominated the proceedings
A selection of looks from the Rihanna for River Island show
90s influences felt strongly in the pieces
Tie-dye was also a dominant feature in the line