DMFC has a serious technical problem, which is called "crossover". The crossover CH3OH, which passes through the polymer electrolyte from the anode to cathode, usually adsorbs on the surface of the cathode catalyst (Pt black) that decreases the DMFC performance. In this study, tetraphenylporphine and tetraphenylporphyrin-metals (metals: Co, Mn and Ru) were thermally decomposed at 673-1173 K for 7.2 ks and the activity of the oxygen reduction of the product was investigated using a rotating disk electrode in order to develop a new cathode catalyst with CH3OH tolerance. The thermally decomposed TPP-Co and TPP-Ru, which have no activity toward CH3OH oxidation, are possible materials as the cathode catalyst of the DMFC, thus being a substitute for the Pt black.