High performance and electrochemically stable Pt/graphene catalysts assisted with polydiallyldimethylammonium (PDDA) have been synthesized for PEM fuel cells. The preparation procedure and properties of the catalysts are investigated in detail. With the introduction of PDDA molecules, Pt nanoparticles can be well-dispersed on graphene support, resulting in improved electrochemical surface area and enhanced electrocatalytic activity. The corresponding electrochemical surface areas (ECSA) of catalyst layers calculated from the hydrogen desorption peak on cyclic voltammogram curves are 78.3, 72.5 and 73.6 cm(2) g(-1) for catalyst layers with Pt/graphene, Pt-PDDA/graphene, and Pt/graphene-PDDA catalysts, respectively. Both PDDA modified Pt nanoparticles and PDDA modified graphene supports also exhibit high durability toward electrochemical oxidation cycles compared with the conventional produced Pt/graphene catalyst at the same conditions. After 3000 cycles, only 23.52% of the initial ECSA remains for Pt/graphene electrocatalyst whereas 43.04% and 37.7% of the initial ECSA for the Pt/graphene-PDDA and Pt-PDDA/graphene catalysts remain, respectively. (C) 2013 Elsevier Ltd. All rights reserved.