Witherspoon was nominated for Best Performance by an Actress in a Motion Picture, Musical or Comedy, at the ceremony for her performance in Election.
The actress, who donned a gorgeous strapless dress to the award show, was nominated alongside Janet McTeer, Julianne Moore, Julia Roberts, and Sharon Stone.
Witherspoon shared a laugh with photographers on the red carpet.
Witherspoon attended the ceremony with her then-husband, Ryan Phillippe.
The actors first met in 1997, a few years before they starred in Cruel Intentions together.
The duo, who tied the knot in 1999, share kids Ava and Deacon Phillippe.
Phillippe and Witherspoon stopped by an after-party following the 2000 Golden Globes.