The 30-year-old actress landed on the red carpet in kinky bondage boots and a high-fashion Tom Ford gown.
But the photographers got another view Anne clearly wasn't wearing any underwear. Whoopsies!
The wardrobe malfunction, or " Les Flasherables", didn't detract from the star's glamorous red carpet appearance, as you can see in the video below.
Anne's bondage stilettos were custom-made for her using "vegan leather", as the actress refuses to eat or wear animal products.
She dazzled again in a more demure dress later that night, arriving to film an interview on The Late Show with David Letterman. Anne hath got style, don't cha think?
The Devil Wears Prada star is widely touted to win Best Supporting Actress at the 2013 Academy Awards for her role as starving prostitute Fantine in Les Mis.
In pics: Celebrity wardrobe malfunctions