Thin films of WOx and Pt on WOx were evaporated onto the microporous layer of a gas diffusion layer (GDL) and served as model electrodes in the polymer electrolyte fuel cell (PEFC) as well as in liquid electrolyte measurements. In order to study the effects of introducing WO, in PEFC electrodes, precise amounts of WOx (films ranging from 0 to 40 nm) with or without a top layer of Pt (3 nm) were prepared. The structure of the thin-film model electrodes was characterized by scanning electron microscopy and X-ray photoelectron spectroscopy prior to the electrochemical investigations. The electrodes were analyzed by cyclic voltammetry and the electrocatalytic activity for hydrogen oxidation reaction (HOR) and CO oxidation was examined. The impact of Nafion in the electrode structure was examined by comparing samples with and without Nafion solution sprayed onto the electrode. Fuel cell measurements showed an increased amount of hydrogen tungsten bronzes formed for increasing WOx thicknesses and that Pt affected the intercalation/deintercalation process, but not the total amount of bronzes. The oxidation of pre-adsorbed CO was shifted to lower potentials for WOx containing electrodes, suggesting that Pt-WOx is a more CO-tolerant catalyst than Pt. For the HOR. Pt on thicker films of WOx showed an increased limiting current, most likely originating from the increased electrochemically active surface area due to proton conductivity and hydrogen permeability in the WOx film. From measurements in liquid electrolyte it was seen that the system behaved very differently compared to the fuel cell measurements. This exemplifies the large differences between the liquid electrolyte and fuel cell systems. The thin-film model electrodes are shown to be a very useful tool to study the effects of introducing new materials in the PEFC catalysts. The fact that a variety of different measurements can be performed with the same electrode structure is a particular strength. (C) 2011 Elsevier Ltd. All rights reserved.