Poly (o-anisidine) (POA) and poly (o-anisidine) / multi-walled carbon nanotube (POA/MWCNT) films prepared upon glassy carbon electrode. Ni (II) is dispersed into POA and POA/MWCNT modified glassy carbon electrode by immersion of the modified electrode in nickel ions solution and used for electrooxidation of methanol in 0.1 M NaOH solution. The results demonstrate that each Ni-POA and Ni-POA/MWCNT modified glassy carbon electrodes behave as an efficient electrocatalyst for the electrooxidation of methanol in alkaline solution. The electrochemical behavior of methanol studied at the surface of Ni-POA and Ni-POA/MWCNT modified glassy carbon electrodes by cyclic voltammetry and chronoamperometry techniques. Combination of POA with MWCNT would offer an attractive support material based on morphological modification and electronic interaction between two components of films onto electrode. The electron transfer coefficient of methanol is determined herein on this two modified electrode by cyclic voltammetry. The generic application of carbon nanotube for electrocatalytic oxidation of methanolis discussed.