Surface chemistry of the electrodes in a proton exchange membrane fuel cell is of great importance for the cell performance. Many groups have reported that electrode preparation condition has a direct influence on the resulting electrode properties. In this work, the oxidation state of electrode components and the composites (catalyst ionomer mixtures) in various electrode structures were systematically studied with X-ray photoelectron spectroscopy (XPS). Based on the spectra, when catalyst is physically mixed with Nafion ionomer, the resulting electrode surface chemistry is a combination of the two components. When the electrode is prepared with a lamination procedure, the ratio between fluorocarbon and graphitic carbon is decreased. Moreover, ether type oxide content is decreased although carbon oxide is slightly increased. This indicates structure change of the catalyst layer due to an interaction between the ionomer and the catalyst and possible polymer structural change during electrode fabrication. The surface of micro porous layer was found to be much more influenced by the lamination, especially when it is in contact with catalysts in the interphase. Higher amount of platinum oxide was observed in the electrode structures (catalyst ionomer mixture) compared to the catalyst powder. This also indicates a certain interaction between the functional groups in the polymer and platinum surface.