In this study, nanoporous nickel phosphate molecular sieves was synthesized by conventional heating for 72 h in the presence of triethylamine as template and characterized by X-ray diffraction (XRD), FT-IR spectroscopy and Filed emission scanning electron microscopy (FESEM). FESEM technique showed the presence of rod-like nickel phosphates VSB-5 and nearly spherical particles with diameters between 30 and 80 nm. The carbon paste electrode (CPE) was modified by nanoporous nickel phosphate molecular sieves and multi-walled carbon nanotubes (MWCNTs) and then Ni2+ ions incorporated to this electrode to obtain Ni-MW–NP/CPE. Electrochemical techniques such as cyclic voltammetry (CV) and chronoamperometry as well as differential pulsed voltammetry (DPV) were applied in order to investigate the role of nickel phosphate molecular sieves and MWCNTs in the electrocatalytic oxidation of ethanol. The current intensity of ethanol oxidation increases impressively on the surface of Ni-MW–NP/CPE and in comparison with Ni-CPE, Ni-MW/CPE and Ni-NP/CPE that means the catalysts can reduce the overvoltage of ethanol oxidation. Some parameters such as potential scan rates and concentration of ethanol investigated to describe the mechanism of ethanol electrooxidation onto Ni-MW–NP/CPE. The values of electron transfer coefficient and mean value of catalytic rate constant for ethanol and redox sites of electrode were found to be 0.844 and 5.76 × 105 cm3 mol−1 s−1, respectively. The good catalytic activity, high sensitivity, good selectivity and stability and ease of preparation rendered the Ni-MW–NP/CPE to be a capable electrode for ethanol electrooxidation.