In this work, Phosphotungstic Acid modified Carbon Paste Electrode (PWA-CPE) is used as a substrate for electro-polymerization of o-Anisidine (OA). Also, Triton X-100 (TX-100) surfactant is used as an additive for electrochemical polymerization of OA onto the PWA-CPE, which is investigated as a novel matrix for dispersion of nickel species. The prepared electrodes are characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and electrochemical methods. Growth of the poly o-Anisidine (POA) film in the absence of TX-100 and/or PWA is very poor, while it considerably increases in the presence of them. The methanol oxidation and stability of the Ni/POA (TX-100)/PWA-CPE are investigated by various electrochemical techniques. It has been shown that the poly (o-Anisidine)/Triton X-100 (POA (TX-100)) at the surface of PWA-CPE improves the catalytic efficiency of the dispersed Ni(OH)2 nanoparticles towards methanol oxidation.