We presented a modified electrode based on electrospun PdO-Co3O4 nanofiber composite for electro-oxidation of methanol in alkaline media. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were adopted to characterize the structures and composition of the composite modified electrodes. The influential factors such as the component and amounts of nanofibers were also studied. After electrochemical pretreatment, the Nafion/PdO-Co3O4/GCE (the atomic ratio of Pd:Co = 2:1) exhibited the greatest electrocatalytic activity toward methanol electro-oxidation among the electrodes investigated. The present novel strategy is expected to reduce the cost of the catalyst of methanol electro-oxidation remarkably. Copyright (c) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.