The pursuit of efficient and stable electrochemical catalysts based on transition metals (TMs) for the hydrogen evolution reaction (HER) is of paramount importance. Herein, a novel partially amorphous NiMoB/NiMoO4-x catalyst with dense nanoparticle assemblies has been prepared with B doping and reduction by one step NaBH4 treatment of smooth nanorod-like NiMoO4 precursor. Benefiting from the MoNi4 alloys partially reduced from NiMoO4 precursor, optimized electronic state through B doping and partially amorphous structure, NiMoB/NiMoO4-x obtained splendid activity for HER with a lower overpotential of 26.2mV at 10mAcm2 coupled with a narrow Tafel slope of 66.75mV dec1, in contrast to NiMoO4 precursor catalyst (260.24@10mAcm2, 149mV dec1) in alkaline solution. Additionally, the self-supported NiMoB/NiMoO4-x electrode exhibits remarkable stability, maintaining a current density of 50mAcm2 for a minimum of 40hours attributed to mixed phases of MoNi4 and amorphous NiMoO4-x for accelerating the H2 evolution and enhancing water adsorption. This work offers a facile avenue to rationally design high-performance electrocatalysts for enhancing hydrogen evolution with NaBH4 accompanying borate doping and reduction.