During the 1980s he turned professional at the age of 13 and began skateboarding for the legendary Powell Peralta Bones Brigade team.
In 1988, Mullen appeared in the feature film Gleaming the Cube, alongside fellow Bones Brigade team members and movie star Christian Slater. Mullen's other videos include The Bones Brigade Video Show, Bones Brigade Video II: Future-Primitive, Bones Brigade Video III: The Search for Animal Chin, and Bones Brigade Video IV: Public Domain.
In the 1990s, Mullen left Powell Peralta and signed on with another skating company, Plan-B. During that decade he improved on the technical area of some of the tricks he performed, and moved from the traditional small freestyle skateboard to the larger, now standard, street skateboard. Mullen was also featured in several Plan-B videos including: The Questionable Video, Virtual Reality, and Second Hand Smoke.
Sometime in the late 1990s Mullen left Plan-B and joined A-Team, starred in the extremely popular Rodney Mullen vs. Daewon Song video series, and continued to push the limits of technical street skating by taking his tricks to new levels of difficulty and new terrain.
Mullen's ability to do the seemingly impossible on a skateboard has earned him the nicknames "The Godfather of Street Skating", "The King of Freestyle" and "The Mutt" by skateboarding fans.