Developing CO-tolerant electrocatalysts is of great importance for the practical use of proton exchange membrane fuel cells (PEMFCs) fed with reforming hydrogen. Transitional metal oxides are a class of promising component to (i) alleviate the CO adsorption on Pt and (ii) provide as a stabilized support for Pt nanoparticles. Herein, we developed an electrostatic assembly strategy to deposit Pt nanoparticles uniformly on the hexagonal tungsten oxides (hex-WO3) modified by polyethleneimine (PEI). It is the first time employing hexWO(3) with biomimetic proton channels and mixed ionic electronic conductivity as supports in PEMFCs. Also, this work is the first report using PEI as a linker to assemble Pt nanoparticles and metal oxide supports. The Pt/PEI-hex-WO3 composites possess excellent dispersion of Pt nanoparticles with average size less than 3 nm even at Pt loadings as high as 40 wt%. The Pt/PEI-hex-WO3 catalysts exhibit superior catalytic activity and electrochemical stability for the hydrogen electro-oxidation (HOR) in the presence of CO, and good PEMFC performance compared to the conventional carbon-supported Pt catalysts, attributed to the bifunctional mechanism and a strong metal-support interaction (SMSI). (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.