Copper nanoparticles were fabricated by electro-reduction of CuSO4 solution in the presence of cetyltrimethylammonium bromide (CTAB) cationic surfactant as an additive through potentiostatic method. The prepared copper nanoparticles were characterized by scanning electron microscopy (SEM) and electrochemical methods. The SEM images reveal that the nanoparticles with diameters at about 70 nm were uniformly dispersed on the electrode surface. Copper oxide nanoparticles modified glassy carbon electrode (nano-CuO/MGCE) was prepared by using consecutive potential cycling between -1.0 to 1.0 V at 100 mVs−1 in 0.1 M NaOH solution. The electrochemical techniques such as cyclic voltammetry and chronoamperometry showed that the nano-CuO/MGCE can catalyze the methanol oxidation in 0.1 M NaOH solution. It has been found that in the course of an anodic potential sweep, the methanol oxidation follows the formation of CuIII and is catalyzed by this species through a mediated electron transfer. Also, the modified electrode was stable for three weeks in dry conditions after repetitive measurements.