The electrooxidation of methanol from alkaline medium at different arrangement of binary catalysts composed of NiOx and MnOx nanoparticles modified glassy carbon electrode (GC) is studied. Different techniques such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) are used for the characterization of those electrocatalysts. The enhancement of the electrocatalytic oxidation of methanol depends essentially on the arrangement and the loading extent of the NiOx nanoparticles. The arrangement in which MnOx is deposited first followed by NiOx nanoparticles (GC/MnOx/NiOx) reveals the best performance. The study is performed under different loadings of the NiOx catalyst and different concentrations of methanol. Minimum loading of NiOx is required to obtain synergism between MnOx and NiOx. The EIS results confirm the above trends and also help to interpret the above conclusions. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.