The Ni-MoO₂ heterostructure was synthesized in suit on porous bulk NiMo alloy by a facile powder metallurgy and hydrothermal method. The results of field emission scanning electron microscopy (SEM), field emission transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) reveal that the as-prepared electrode possesses the heterostructure and a layer of Ni(OH)₂ nanosheets is formed on the surface of Ni-MoO₂ electrode simultaneously after hydrothermal treatment, which provides abundant interface and much active sites, as well as much active specific surface area. The results of hydrogen evolution reaction indicate that the Ni-MoO₂ heterostructure electrode exhibits excellent catalytic performance, requiring only 41 mV overpotential to reach the current density of 10 mA/cm². It also possesses a small Tafel slope of 52.7 mV/dec and long-term stability of electrolysis in alkaline medium.