Co-W alloys are developed by an electroplating technique using a bath solution which contains triammonium citrate (TAC) and dimethyl sulfoxide (DMSO) under suitable plating conditions. The alloys are characterized by polarization studies in order to determine their prospects as effective anode materials for methanol fuel cells in both acidic and alkaline media. Scanning electron microscopic and X-ray diffraction analysis shows that the coatings are partially amorphous. The alloys exhibit low overvoltage even on prolonged electrolysis, and have good corrosion resistance in acidic and alkaline media. Electrochemical parameters for methanol oxidation depend on the heat treatment, deposition potential and microstructure of the deposit. © 2002 Elsevier Science B.V. All rights reserved.