Hollow graphitic carbon spheres (HGCSs) with a high surface area are produced by the carbonization of hollow polymer spheres obtained by the polymerization of core/shell-structured pyrrole micelles. HGCSs are employed as a carbon support material in a direct methanol fuel cell catalyst, and their effect on the electrocatalytic activity toward methanol oxidation is investigated. Pt catalyst supported on HGCSs shows a better electrocatalytic activity compared to that on Vulcan XC-72, which has been commonly used in fuel cell catalysts. The observed enhancement in the electrocatalytic activity is attributed to the improved electronic conductivity and high surface area of HGCSs.