ABSTRACT Heterostructure materials have been widely applied in electrocatalytic hydrogen evolution reaction (HER) due to the special properties, and amorphous materials also are attractive for researchers because of the good catalytic performance. Herein, an amorphous‐NiCoP/crystalline Ni 3 S 2 catalyst of heterojunction structure (HE‐NiCoP/Ni 3 S 2 ) is synthesized by two‐step method consisting of hydrothermal and electrodeposition processes. HE‐NiCoP/Ni 3 S 2 catalyst exhibited excellent catalytic performance with the overpotentials of 70 and 148 mV at 10 and 100 mA cm −2 , respectively (1 m KOH), owing to the strong electronic coupling and the reconstruction effect around heterostructure interface. Compared with crystalline‐crystalline structure, the d‐band center of the amorphous‐crystalline heterostructure moved up to optimize the valence state and H adsorption of HER, thereby enhancing the catalytic performance. This work provides a promising strategy for preparing amorphous‐crystalline heterostructure catalysts and optimizing the catalytic activity, which can be implemented for other transition metal compound electrocatalysts.