AbstractNickel‐cobalt bimetal phosphides were prepared via the phosphidation treatment of NiCo‐based Prussian blue analogue (PBA). Subsequently, the core‐shell structures of NiCoP@MoS2 were successfully assembled through a solvothermal reaction, where the NiCoP substrates were uniformly and randomly covered by MoS2 nanosheets. The resulting hybrids exhibited significantly superior catalytic activities towards hydrogen evolution reaction (HER) in 0.5 M H2SO4 to bare MoS2. The optimal catalyst afforded the best HER performance with a low overpotential of 138 mV at 10 mA cm−2 and Tafel slope of 78.1 mV dec−1, together with high stability and durability. The excellent HER properties of hybrids mainly originated from the unique core‐shell architecture and the intrinsic natures of MoS2 and PBA‐derived bimetal phosphides.