To design a catalyst for the dissociation of H-2 with better CO-tolerance performance is very important for proton exchange membrane fuel cells (PEMFCs) towards high efficiency. With slab model, the catalytic properties of overlayer Pt on Cu substrate (Pt/Cu) are analyzed by first-principle calculations. The CO saturation coverage (40%) on Pt-2/Cu is found to be lower than that of pure Pt (about 75%). The dissociation barrier from H-2 to H is less than 0.4 eV under the saturation coverage of CO. On the basis of kinetics of proton formation, the CO-tolerance ability on double-layer Pt with Cu is found to be greatly improved compared with that on pure Pt. It is expected that Pt overlayer on Cu(111) is a potential anode material with lower cost for PEMFCs. (C) 2018 Elsevier B.V. All rights reserved.