Dual metal oxides immobilized on amine functionalized fly ash coated conducting copolymer composite as the catalyst supporting material has been prepared. Here, a facile method has been employed to prepare nickel nanoparticles deposited hybrid nano composite with unique morphology (Ni/Poly(Py-co-O-Anis)/ZnO/CuO/AFA). The resulted composite material has been characterized by different analytical techniques like scanning electron microscopy, transmission electron microscopy, X-ray diffraction, BET, EDX, elemental dot color mapping and infrared spectroscopy. Further, electrochemical performance of Ni/Poly(Py-co-O-Anis)/ZnO/CuO/AFA modified graphite electrode has been investigated for methanol and sodium sulphide electrooxidation by cyclic voltammetry, linear sweep voltammetry and chronoamperometric measurements. From electrocatalytic studies, it was found that the hybrid Ni/Poly(Py-co-O-Anis)/ZnO/CuO/AFA electrode shows superior catalytic activity compared with Ni/Poly(Py-co-O-Anis) catalyst. In addition, nanorods/nanosheets structure were obtained for hybrid composite through a simple room temperature reaction. In order to generate energy, the single stack test alkaline fuel cell has been carried out and results show the maximum power density of 103.24 and 44.75 mWcm(-2) for methanol and Na2S, respectively. From the overall results, it has been concluded that the prepared Ni/Poly(Py-co-O-Anis)/ZnO/CuO/AFA is a potent, non-precious and low cost catalyst with an improved catalytic activity in direct alkaline fuel cells. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.