Although it suffers from a heavy dependence on the noble platinum catalyst, the electrochemical hydrogen evolution reaction (HER) is one of the most promising methods for the production of hydrogen. After numerous efforts, it is found that MoS2-based heterostructure may replace platinum as the electrochemical HER catalyst. In this work, the nanocrystalline NiSe2/MoS2 heterostructures were successfully prepared on the carbon fiber paper (CFP) substrate through electrochemical deposition and hydrothermal process. According to a series of electrochemical HER tests and a comparison with other MoS2-based heterostructure catalysts, the CFP/NiSe2/MoS2 catalyst with an overpotential η10 of 143 mV and a Tafel slope of 45 mV dec−1 exhibited an excellent electrochemical HER catalytic performance and durability. In addition, CFP/NiSe2/MoS2 catalyst was treated by plasma to further improve the catalytic performance of the catalyst. [ABSTRACT FROM AUTHOR]