A low-energy methodology has been proposed to synthesized Ni-based binary and ternary compounds from M-acetylacetonates (M = Ni, Co and Cu) and mechanical milling (MM) to be used as electrocatalysts for the methanol oxidation reaction in alkaline medium (1 M KOH). The strategies used in this study expand the possibilities of obtaining materials with efficient electrocatalytic activities from noble metal-free catalysts, while reducing the production cost. The prepared electrodes were characterized to evaluate changes in the thermal decomposition, as well as chemical, structural, morphological and microstructural changes with the composition. Electrochemical performance was evaluated by conventional methods such as cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The series of Ni-based catalysts demonstrated that after MM the composites integrate with oxides of the individual metallic materials without the formation of solid solutions. The electrocatalytic mass activities of the as-obtained composites were found in the following order: Ni0.80Co0.10Cu0.10/C (1181.14 A/g) ≅ Ni0.8Cu0.2/C (1124.45 A/g) > Ni0.80Co0.05Cu0.15/C (254.50 A/g) > Ni0.80Co0.15Cu0.05/C (209.34 A/g) > Ni0.8Co0.2/C (136.64 A/g). Among them, Ni0.80Co0.10Cu0.10/C showed the greatest stability and the leastwest charge transfer resistance that ranges between 0.28 and 0.80 Ω depending on the methanol concentration, and also presented activities higher than those of the commercial Pt/C catalysts. The results demonstrate that with this simple method, it is possible to modulate the electronic structure reducing CO poisoning on the surface of the catalysts and act as an alternative to replace high-cost noble metals during energy conversion from methanol.