Here, novel polyvinyl alcohol (PVA) nanofibers with incorporated CuO and Co3O4 nanoparticles (PVA-CuO-Co3O4) were synthesized through a conventional single-nozzle electrospinning technique and characterized by atomic force microscopy (AFM), energy dispersive X-ray analysis (EDX), fourier-transform infrared spectroscopy (FT-IR), elemental analysis, transmission electron microscopy (TEM), differential thermal analysis (DTA), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). Novel Pt/polyvinyl alcohol-CuO-Co3O4/chitosan (Pt/PVA-CuO-Co3O4/CH) catalyst was successfully prepared. EDX, TEM, and FT-IR spectroscopy techniques were used to characterize the prepared catalysts. The electrocatalytic activity of Pt/PVA-CuO-Co3O4/CH catalyst was investigated for methanol electrooxidation through cyclic voltammetry, chronoamperometry, CO stripping voltammetry, and electrochemical impedance spectroscopy techniques. The effects of some experimental factors for methanol electrooxidation were studied on the prepared catalysts and the optimum conditions were determined. Pt/PVA-CuO-Co3O4/CH catalyst had extraordinary electrocatalytic activity for methanol electrooxidation. It exhibited better stability, higher electrochemically active surface area, and better antipoisoning effect than Pt/PVA-CuO-Co3O4 and Pt/PVA/CH catalysts indicating that Pt/PVA-CuO-Co3O4/CH could be a promising catalyst for direct methanol fuel cell (DMFC) applications. A real DMFC was designed, assembled and tested with Pt/PVA-CuO-Co3O4/CH as anodic catalyst. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.