In this work, TiO2 nanotubes were synthesized electrochemically by anodization of pure Ti sheet in 0.5% HF and annealed in N2 atmosphere to obtain (TiO2 NTs‐N2) and then the nickel was deposited on the support TiO2 NTs by immersing TiO2 NTs in mesoporous sol–gel template Ni nanoparticles method for overnight and then annealed in N2 atmosphere to obtain the electrocatalyst NiO NPs/TiO2 NTs‐N2. The physicochemical characterizations of NiO NPs/TiO2 NTs‐N2 were performed by scanning electron microscopy (SEM) and X‐ray diffraction (XRD) analysis. The catalyst NiO NPs/TiO2 NTs‐N2 was electrochemically characterized in a basic solution of methanol by cyclic voltammetry (CV) measurement. XRD characterization indicates the presence of nickel oxide nanoparticles with a diameter less than 43 nm and regularly combined into TiO2 nanotubes. NiO NPs/TiO2 NTs‐N2 catalyst exhibited a remarkably high electrocatalytic activity and has high electrocatalytic stability for methanol electrocatalytic oxidation reaction. The electrochemical studies showed that NiO NPs/TiO2 NTs‐N2 in alcoholic basic solution exhibited higher catalytic activity and stronger poisoning tolerance for methanol oxidation than that in nonalcoholic basic solution. This suggests that the NiO NPs catalyst supported on TiO2 NTs‐N2 has promising potential applications in electrocatalyst reactions. Nickel oxide supported on the conductive support TiO2 NTs‐N2 is used as an electrocatalyst in alkaline fuel cells. Results showed the best improvement in the physico‐chemical properties of these catalysts in comparison with previous studies.