Hydrogen production by electrocatalytic water splitting is a pollution-free, energy-saving, and efficient method. The low efficiency of hydrogen production, high overpotentials and expensive noble-metal catalysts have limited the development of hydrogen production from electrocatalytic water splitting. Therefore, the exploration of bifunctional electrocatalysts for water overall splitting to produce hydrogen is of profound significance. Herein, Ni3S2@Ni2P/MoS2 heterostructure electrocatalysts were synthesized on Ni foam through an environmentally friendly hydrothermal method and low-temperature phosphating method. The synergistic effects between different components and the mutual substitution principle between sulfur atoms and phosphorus atoms greatly improve the OER performance of the electrocatalyst. It is also an effective strategy to optimize the adsorption energies of intermediates by the design of heterostructured catalysts composed of multiple substances. Ni3S2@Ni2P/MoS2 only requires a low overpotential (η10) of 175 mV at a current density of 10 mA cm-2 in 1.0 M KOH solution and the stable duration exceeds 40 h. In addition, this heterogeneous structure is assembled into an electrolytic cell for overall water splitting, which exhibits a low cell voltage of 1.61 volts and retains the robust stability over 30 h at 10 mA cm-2. The Ni3S2@Ni2P/MoS2 heterostructure prepared in this research provides a strategy for exploring other heterostructured electrocatalysts with different components.