In the present study, TiO2 nanoparticles are used as inorganic nanofiller material to prepare nanocomposite proton exchange membrane (PEM). Sulfonated polyvinyl alcohol (SPVA) is synthesized by 4-formylbenzene-1,3-disulfonic acid disodium salt hydrate and water. The cross-linking reaction is performed by glutaraldehyde. These membranes were then dip coated with polyacrylic acid and chitosan alternately and one layer-by-layer (LBL), two LBL and three LBL membranes were prepared. The chemical structure evaluation of SPVA membrane is performed using FTIR. The direct methanol fuel cell (DMFC) catalysts of 10Cu/CeO2 and 10 Pt-10 CeO2/C were prepared by reduction reaction and hydrothermal technique. Thus obtained material was spin coated on 2 x 2 cm(2) carbon paper to prepare catalyst anode/cathode. The morphology, size, and purity of catalyst particles are analysed by SEM, UV visible spectroscopy, FTIR and EDS. Electrochemical analysis is also done to test the performance. Results show that Cu/CeO2 catalyst shows excellent catalysis towards methanol oxidation, which is better than 10 Pt-10 CeO2/C particles. The 10Cu/CeO2 catalyst gives peak voltage of 915 mV for infinite resistance, which is higher than the reported value of the conventional 20 Pt/C catalyst (810 mV). (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.