She chose her stage name to reflect her love of Mötley Crüe, whose bassist, Nikki Sixx, named his daughter Storm. In 2009 a recruitment effort led her to consider challenging incumbent David Vitter for the 2010 Senate election in her native Louisiana.

Daniels began stripping at age 17 at a club in Baton Rouge then expanded to become a feature performer in September 2000. While working as a feature she met with Devon Michaels, who was doing lesbian scenes in a pair of upcoming movies — one for Wicked Pictures and one for Sin City, and invited Daniels to accompany her.¹⁰ Daniels accompanied Michaels to her Wicked shoot, where she met Brad Armstrong and co-starred with Michaels in her Sin City scene, American Girls Part 2. Afterwards, Armstrong invited Daniels to stay out with him where she continued doing lesbian-only scenes.

In July 2002, she was cast as the lead in a feature film for Wicked Pictures called Heat, where she did her first heterosexual sex scene, and in September of the same year she signed an exclusive contract with Wicked. In 2004 she won the Best New Starlet Award from Adult Video News, which was a complete surprise to Daniels, as she was so sure Jesse Jane would win she made a $500 bet with another porn starlet. She has directed for Wicked since 2004, and is their leading performer.

She has appeared in several men's magazines including Playboy, Hustler, Penthouse, High Society, GQ, and FHM. She has also written for FHM. Daniels also appeared in an episode of Real Sex where she is seen participating in 2001 Miss Nude Great Plains Contest. In early 2007, she appeared in Dirt on the FX Network, where she played a stripper who helps to set up a basketball player played by Rick Fox. Later in 2007 Stormy Daniels appeared in Maroon 5's music video for their song “Wake Up Call” as a pole dancer. She appears in the film The 40-Year-Old Virgin as the main character watches her in the video Space Nuts: Episode 69—Unholy Union, and then tries dreaming about her. She also plays a Las Vegas lap dancer in Knocked Up, alongside fellow porn star Nautica Thorn. A deleted scene on the Virgin DVD includes her having dinner with producer Seth Rogen in a parody of My Dinner with Andre. She also appears in the fifth episode of the show Party Down.