The preparation of highly efficient and stable non-precious metal catalysts is essential for the development of electrocatalytic water-splitting to produce high-purity hydrogen. In this work, NiMo/TNAs nanohierarchical arrays were constructed by simple anodic oxidation and electrodeposition route, The research of its hybrid cocatalyst is envisioned to bestow more active sites with appropriate crystal engineering and modi?ed electronic properties for enhancing catalytic performance. NiMo alloy is firmly coated on the unique curved and ordered interface of TiO₂ nanotube arrays (TNAs) by electrodeposition, When the deposition current and the concentration of Mo ions in the electrolyte change, the state and catalytic ability of NiMo in TNAs also change,the study proved that the samples prepared by depositing 1 min under the parameters of deposition current density of 15 mA.cm^_-2 and Mo ion concentration of 4g.L^_-1 show higher HER catalytic performance. The electrode exhibits the relatively small onset overpotential of 55 mV and presents an overpotential of 110 mV and 227 mV at 10 mA.cm^_-2 and 100mA.cm^_-2 HER current density, also remained an excellent stability with no performance degradation after scanning for 15h at a constant potential. NiMo alloy particles deposited on the curved sidewalls with uniform distribution of TNAs is demonstrated to be an effective method to prepare the cheap and efficient electrocatalyst.