Electrocatalytic hydrogen production, to produce hydrogen (H2) and oxygen (O2) at the same time through hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), which is considered as an efficient and environmentally friendly way to produce hydrogen. However, the high-efficiency catalysts for commercialization are expensive and have limited reserves, which limit the large-scale application of electrolytic water technology. Therefore, the development of efficient electrocatalysts with low cost, high stability and environmental friendliness, especially phosphides based on non-precious metal materials, is very challenging and much desired. Here, Mo-doped Ni5P4 catalysts with hollow nanoflower structure were successfully prepared by hydrothermal and relatively low phosphorylation temperature. The microstructure of Mo-Ni5P4 catalysts was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and the electrochemical properties of Mo-Ni5P4 materials were investigated. The results show that, catalysts synthesized in this work promote the rate of the HER water dissociation step, taking advantage of the Mo and Ni5P4 hollow structures change and the large surface area of the porous nanosheets. In alkaline electrolytes, Ni5P4 under Mo loading requires only 116 mV of hydrogen evolution overpotential to achieve a current density of 10 mA·cm-2, while only 255 mV of oxygen evolution overpotential is required. In a two-electrode configuration, a battery voltage of only 1.608 V is required. The catalyst still shows good stability after 27 h of continuous testing.