The amorphous nano-Nd-Ni-B rare earth (RE) alloy catalytic electrode on nickel foam (NF) was prepared by simple one-step electroless deposition method and served as a highly active hydrogen evolution reaction (HER) catalyst. Its microstructure and electrocatalytic HER performance were characterized. The results show that addition of Nd improved the electrocatalytic HER. The preparation conditions were optimized with neodymium nitrate of 3 g∙L^-1, reaction temperature of 35 ℃ and reaction time of 1 h. The Nd-Ni-B/NF electrode requires an overpotential of only 180 mV to achieve the current density of 20 mA∙cm^-2 in 1.0 mol∙L^-1 KOH solution, and the corresponding Tafel slope is 117 mV∙dec^-1. HER of Nd-Ni-B/NF catalyst is controlled by Volmer-Heyrovsky step. Moreover, the Nd-Ni-B/Nf shows superior electrochemical stability, 12 h chronoamperometry and 2000 sweeps of cyclic voltammetry with no obvious activity decay.