This study demonstrates the feasibility of platinum-free catalysts, which exhibit not only a high activity in the oxygen reduction reaction (ORR) but also a high tolerance of methanol. A cobalt (II) tetramethoxyphenylporphyrin (CoTMPP) precursor was dispersed in N,N-dimethylmethanamide (DMF), which was ultrasonically stirred for 30 min to yield a homogeneous solution, and then filtered to remove the solvent. The CoTMPP precipitate was pyrolyzed at temperatures of 300, 500, 700 and 900 degrees C in N(2) atmosphere. Raman spectra include strong peaks at 1330 and 1550 cm(-1), which are associated with the D- and G-peaks of pyrolyzed CoTMPP above 500 degrees C, revealing that the original porphyrin structure of CoTMPP yields a network structure of poly-aromatic hydrocarbons upon the pyrolysis. Pyrolyzed CoTMPP loaded on carbon blacks (CoTMPP/C) at 700 degrees C exhibits a higher ORR activity than other various pyrolysis temperatures. In a methanol-containing solution, pyrolyzed CoTMPP/C preferentially undergoes the ORR rather than the methanol oxidation reaction, and so exhibits a high tolerance of methanol. Pyrolyzed CoTMPP has the pyrrolic nitrogen, and part of the cobalt-containing nitrogen chelate is cleaved and bound to other atoms, forming Co-N(x)-C(y(x+y=4),) which are responsible for the ORR activity and the high tolerance of methanol. (c) 2011 Elsevier BM. All rights reserved.