Jaymes' adult film career began in the summer of 2002.
Her stage name is a combination of her real first name, Jessica, and the first name of her then-lover, James. In 2004 she became Hustler's first contract model and the "Hustler Honey of the Year". In August 2008 she was the Penthouse Pet of the Month.
Jaymes played a small role in two episodes of the television series Weeds, and made an appearance in the VH1 reality show Celebrity Rehab Sober House.