The Ni-B-modified carbon paste electrodes were synthesized by the electroless deposition, followed by thermal treatment. Scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy were performed to gather information about the morphology, crystallinity, and binding energy. The fabricated Ni-B/C electrodes are applied to methanol electrooxidation in alkaline media. The results show that Ni-B/C catalyst with a comparable amount of microcrystalline Ni and Ni3B, 59 and 41 wt%, displayed a significantly enhanced electrocatalytic activity, which is approximately three times the activity of the unheated Ni-B/C catalyst. The synergetic mechanism of methanol oxidation was proposed that involves one Ni3B site favor the adsorption and activation of the methanol molecule and one Ni site for oxidative mediation of methanol. In addition, the kinetic parameters of the reaction were calculated using linear sweep voltammetry. The illustration of the speculated methanol oxidation mechanism. [GRAPHICS]