Improving water adsorption and hydrogen (H) atoms desorption capacities are critical issues for the hydrogen evolution reaction (HER) in alkaline media. Herein, a ReS2/NiS heterostructure was generated in situ on the surface of the nickel foam (NF) using a facile hydrothermal process. The combination of experimental and density functional theory (DFT) analyses revealed a charge transfer from NiS to ReS2, which directly promoted water adsorption on Ni sites in NiS as well as H desorption on S sites in ReS2. Moreover, the antioxidation capacity of the heterointerface in the catalyst improved. Therefore, the formed ReS2/NiS@NF delivered an excellent HER activity very close to that of commercial Pt/C at low current density with overpotential of 78 mV at 10 mA/cm2 while remarkably outperforming Pt/C at high current densities. The ReS2/NiS@NF also exhibited remarkable stability at 150 mA/cm2. This work provides a strategy for designing excellent electrocatalysts based on NiS.