Abstract: The 2D layered structured material of Molybdenum disulfide have drawn more and more attention due to its unique structure, but the performance enhancement of MoS₂ for the hydrogen evolution reaction and the preparation of catalysts with specific morphologies still need further exploration. In this work, polypyrrole (PPy) modified molybdenum sulfide and molybdenum oxide ternary nanohybrids composite catalysts (MoO_x-MoS₂/PPy) were obtained via coupling hydrothermal method and in situ oxidative polymerization. In addition, the amount of the reactants, the concentration of surfactant were adjusted to regulate the morphology and structure of catalysts, and MoO_x-MoS₂/PPy catalysts were used as the electrode material for the electrochemical performance under three-electrode system. Moreover, The structured MoO_x-MoS₂/PPy catalysts was well characterized by XRD, SEM, TEM, BET and XPS techniques. The results show that the edge curling with petaloid lamination structure of MoO_x-MoS₂/PPy21 catalyst exhibits high dispersion, and the MoO_x-MoS₂/PPy21 catalyst has superior overpotential (123 mV @ 10 mA/ cm²) and Tafel slope (75.9 mV/ dec). Thus, MoO_x-MoS₂/PPy21 ternary nanohybrids composite catalysts may open up a new way to the application of molybdenum disulfide composite in electrocatalytic hydrogen evolution.