We have analyzed the electronic structure of carbon alloy cathode catalysts alternative to platinum-based materials for polymer electrolyte fuel cells using synchrotron radiation techniques. A series of X-ray absorption and X-ray photoemission spectra of FePc-based carbon alloy catalysts pyrolyzed at various temperatures clearly show the turnover of chemical species dependent on the pyrolysis temperature. We can feed back the above information to synthesis of advanced catalysts with much higher activity and durability.