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Molybdenum disulfide (MoS 2) exhibits the modest properties toward hydrogen evolution due to its poor electrical conductivity and a limited number of active sites. To make up for the defects in MoS 2 , we built hierarchical P-doped MoS 2 /NiS 2 @carbon hollow nanospheres (P–MoS/NiS@CHNS) electrocatalyst via one-step hydrothermal method owning to the priority of the reaction between Ni2+ and H 2 S. Motivated by high-efficient electron transfer at the interface of heterostructure and the activation of MoS 2 by P dopant, P–MoS/NiS@CHNS exhibits optimal Gibbs free energies (ΔG H∗) and superior HER performance with low overpotential (ƞ 10) of 110 ​mV ​at 10 ​mA ​cm−2 and small Tafel slope of 61 ​mV dec−1. The focus of this work is to optimize the HER performance of MoS 2 through P-doping and heterostructure construction, which can further provide a reference for the design of MoS 2 based catalysts. Image 1 • The P–MoS 2 /NiS 2 heterostructure is in favor of expeditious electrons transfer. • Thanks to the priority of the reaction between Ni2+ and H 2 S, the heterostructure was constructed. • The introduction of P optimizes the electron configuration of MoS 2. • The well-designed P–MoS/NiS@CHNS electrocatalyst has the optimal ΔG H∗ and E a value. [ABSTRACT FROM AUTHOR]