A novel cathode catalyst for direct methanol fuel cell, MN4 polymeric cobalt tetrametho -xyphenyl porphyrin (PCoTMPP), was prepared by solvent thermal method. The PCoTMPP exhibited spherical particles with diameter of 0.8~1µm. The spherical PCoTMPP showed a good monodisperse. The oxygen reduction reaction activity of PCoTMPP was examined by CV, LSV and CA methods. The results showed that PCoTMPP has a better oxygen reduction reaction activity and stability in comparison with CoTMPP and leads to a four-electron reduction of dioxygen to water.