Abstract We report on the electronic structure of three different types of N-containing carbon-based cathode catalysts for polymer electrolyte fuel cells observed by hard X-ray photoemission spectroscopy. Prepared samples are derived from: (1) melamine and poly(furfuryl alcohol), (2) nitrogen-doped carbon black and (3) cobalt phthalocyanine and phenolic resin. C 1 s spectra show the importance of sp 2 carbon network formation for the oxygen reduction reaction (ORR) activity. N 1 s spectra of the carbon-based cathode catalysts are decomposed into four components identified as pyridine-like, pyrrole- or cyanide-like, graphite-like, and oxide nitrogen. Samples having high oxygen reduction reaction activity in terms of oxygen reduction potential contain high concentration of graphite-like nitrogen. O 1 s spectra are similar among carbon-based cathode catalysts of different oxygen reduction reaction activity. There is no correlation between the ORR activity and oxygen content. Based on a quantitative analysis of our results, the oxygen reduction reaction activity of the carbon-based cathode catalysts will be improved by increasing concentration of graphite-like nitrogen in a developed sp 2 carbon network.