The electronic structure of Co atoms in cobalt phthalocyanine (CoPc)-based carbon catalysts, which were prepared by pyrolyzing a mixture of CoPc and phenol resin polymer up to 1000 degrees C, has been investigated using X-ray absorption fine structure (XAFS) analysis and hard X-ray photoemission spectroscopy (HXPES). The CoK XAFS spectra show that most of the Co atoms are in the metallic state and small quantities of oxidized Co components are present in the samples even after acid washing to remove Co atoms. Based on the difference in probing depth between XAFS and HXPES, it was found that after acid washing, the surface region with the aggregated Co clusters observed by transmission electron microscopy is primarily composed of metallic Co. Since the electrochemical properties remain almost unchanged even after the acid washing process, the residual metallic and oxidized Co atoms themselves will hardly contribute to the oxygen reduction reaction activity of the CoPc-based carbon cathode catalysts, implying that the active sites of the CoPc-based catalysts primarily consist of light elements such as C and N. (C) 2011 Elsevier B.V. All rights reserved.