In this work, polyvinyl alcohol/cupric acetate nanofibers are prepared by electrospinning method and copper oxide nanoparticles (CuO-NPs) are produced after thermal treatment. The morphology and structure of the materials are characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), nitrogen adsorption-desorption isotherm (BET) and electrochemical impedance spectroscopy (EIS). The CuO-NPs prepared by calcination of the nanofibers in air at 500 C are used as potent catalysts for hydrazine hydrate electrooxidation. The results demonstrate that the renewable CuO-NPs modified carbon paste electrode (CPE) exhibits high electrocatalytic activity and good performance towards hydrazine hydrate oxidation. The electrocatalytic performance of the firmly embedded CuO-NPs is attributed to high surface areas as well as chemical inertness of the carbon-based electrode.