The actress stunned in this sleek asymmetrical strapless number by Giambattista Valli at the 2011 Kennedy Center Honors.
Anne definitely brought us back to The Princess Diaries days when she arrived at the 2010 Met Costume Institute Gala in this ethereal Valentino gown!
This gorgeous gold Armani was the perfect gown for the the 2011 Golden Globes.
This bold blue Armani Prive that Anne wore to the 2009 Golden Globes was a little bit out of the box for Bride Wars star, but we loved the look!
This mermaid-style Armani Prive that the actress wore to the 2009 Oscars was a big "win" in our book!
Anne looked absolutely angelic in this white, flowy frock from Bill Blass's Fall 2008 collection for the Get Smart premiere in Rome.
This sexy red Valentino was one of seven dresses that Anne wore at the 2011 Academy Awards!
This stunning Atelier Versace turned a lot of heads at the 2008 Venice Film Festival...although the actress' gorgeous gams might have had a little something to do with it, too!
Anne looked absolutely angelic in this gorgeous Chanel gown at the 2013 Golden Globes.
This bondage-inspired S&M look by Tom Ford was totally out of character for the class-act actress and we loved everything about it! What's even cooler is the shoes were made specially so that they didn't conflict with the dedicated vegan's lifestyle.
Watch the Golden Globes on Sunday on NBC at 8 p.m. ET/5 p.m. PT