Ultraviolet-visible and fourier transform infrared absorption spectra indicate that poly-tetraphenylporphyrin Co (II) (PTPPCo) can be obtained by heat-treating 5,10,15,20-tetra (4-carboxyphenyl)-porphyrin Co (II) (TCPPCo) at 400 degrees C in argon atmosphere. Polytetraphenylporphyrin Co/C is obtained by heat treatment (HT) of TCPPCo, which is adsorbed on Vulcan XC-72 with different Co-N(4) loading, from 400 degrees C to 1000 degrees C in argon atmosphere. Catalysts are evaluated for electroreduction performances of oxygen on modified electrodes in sulfuric acid solutions. Results from electroreduction of the catalyst (HT 600 degrees C and 6 wt% Co-N(4) loading) show the original reduction voltage is 0.81 V versus the reversible hydrogen electrode, and the transfer electron number is 3.83. The morphology, distribution, and surface elemental analysis of the catalysts are characterized by x-ray diffraction spectroscopy and transmission electron microscopy with energy dispersive x-ray. PTPPCo can homogeneously anchor on the carbon support and withstand decomposition upon heat treatment at 600 degrees C. Since TCPPCo results in polymerization on XC-72, pi (pi) bond increases significantly with the decrease in pi-electron delocalization energy. Improved capacity in electron gain or loss is observed, and the center of electrocatalysis is clearly exposed. Thus, the activity, stability, and selectivity of the catalyst presented in this paper are proven better than those of other common catalysts. (c) 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.