The singer - who was crowned 2014 Fashion Icon of the Year at the New York City event - walked the red carpet in a daring custom-made Adam Selman dress, which was embedded with over 230,000 Swarovski crystals and described as a "scandalous" choice by the designer himself.
The translucent ensemble left little to the imagination and was accessorised with a matching do-rag, a pink Pologeorgis fur stole, Manolo Blahnik shoes and jewellery earrings by Paul Morelli.
Adam told Style.com: "We definitely wanted to make it a little bit scandalous. The dress is just fishnet and crystals and a couple of fingers crossed. But fashion is about beauty, and the [female] body is part of that."
The pair first came up with the idea when they were dressing Rihanna for the MTV Movie Awards last month.
He added: "We started talking about it, and I sketched it shortly after. It brings such a Rihanna feel to the whole thing. It seals the deal."
Rihanna's stylist Mel Ottenberg said staff stayed up until the early hours of the morning adding the final touches to the look.
He explained: "So many people didn't sleep last night. I would say at least eight people worked non-stop from 8pm last night to 3pm today putting on the finishing touches.
"It's so naked. I don't know if it's shocking--I'm with her all the time, so my shock gauge is off, but I told her that I thought she was ready for this dress a while ago, and that I wasn't. I'm the prude, and I'm just catching up."
Rihanna certainly lived up to expectations after being dubbed the "most exciting ambassador in recent memory" by Steven Kolb, the Council of Fashion Designers of America's CEO.