The feasibility of using poly(3,4-ethylenedioxythiophene) (PEDOT) as Pt catalyst support for direct methanol fuel cell (DMFC) anodes was investigated. Measurements with freshly prepared Pt-PEDOT/C electrodes showed poor activity for methanol oxidation in a half-cell and a DMFC. A substantial enhancement in that activity was evident after either electrochemical over-oxidation of PEDOT or long-time storage of the Pt-PEDOT/C gas diffusion electrode (GDE) in air. Both procedures led to a reorganization and increase in porosity of the reaction layer, which obviously contributed to better methanol accessibility to Pt catalyst active centres. The effects of electrochemical activation and long-time storage in air on the morphology and elementary composition of the Pt-PEDOT layer were investigated by means of Hg porosimetry and SEM/EDAX. It was found that the increase in porosity was due to degradation of PEDOT characterized by a significant depletion of sulphur and oxygen in the conducting polymer matrix.