A surfactant-free synthetic methodology is reported for the preparation of β-Ni(OH)2-NiCo2O4 hybrid nanostructure. For comparative study, β-Ni(OH)2-NiO, β-Ni(OH)2-Co3O4, NiCo2O4, NiO, Co3O4, and β-Ni(OH)2 were also synthesized. Materials were characterized by X-ray diffraction, nitrogen sorption, scanning electron microscopy, and transmission electron microscopy. The electrochemical oxidation of methanol is investigated at β-Ni(OH)2-NiCo2O4 modified electrode in the alkaline medium using cyclic voltammetry (CV) and chronoamperometry methods. A detailed investigation is made for the electro-catalytic oxidation of methanol by varying several reaction parameters such as potential scan rate, methanol concentration, etc. Mechanism of methanol oxidation is proposed based on the CV and double steps chronoamperometry studies. β-Ni(OH)2-NiCo2O4 modified electrode exhibited comparatively higher electro-catalytic activity in the methanol oxidation when compared to other modified electrodes investigated in this study.