The stable aqueous dispersion solutions of polymer-modified graphene were prepared by reduction with hydrazine hydrate in situ from exfoliated graphite oxides in the presence of poly (diallyldimethylammonium chloride) (PDDA) and poly(sodium 4-styrenesulfonate) (PSS), respectively. The multilayer films consisting of PDDA-GN and PSS-GN were fabricated on the substrate by layer-by-layer self-assembly technique and characterized by ultraviolet-visible spectroscopy (UV-vis). The multilayer films were used as a novel catalyst support for electrodeposition of Pt nanoparticle clusters in situ. X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscope (FE-SEM), and X-ray diffraction (XRD) analysis demonstrated that Pt particles had been immobilized on the surface of [PDDA-GN/PSS-GN}(n) multilayer films. Cyclic voltammetry and chronoamperometric curves were used to study electrocatalytic activity of Pt/(PDDA-GN/PSS-GN)(n) multilayer films regarding methanol oxidation. The results indicated good electrocatalytic activity of the titled multilayer composites toward methanol oxidation in the 0.5 M H2SO4. (C) 2012 Elsevier Inc. All rights reserved.