Herein, porous Ni3B for efficient HER electrocatalysis can be large-scale prepared by one step sintering method using pure Ni and B powders at different temperatures in the Ar gas. Among them, Ni3B sintered at 850 degrees C (Ni3B-850) demonstrates the best HER activity with a low overpotential of 79 mV at current density of 10 mA cm(-2) for HER in 0.5 M H-2 SO4 electrolyte, Tafel slope of 85.32 mV dec(-1), and outstanding stability. The excellent electrocatalytic activity due to porous and similar core@shell (Ni3B@NiO/Ni(OH)(2) ) structure, which provides larger active surface area, exposes more active sites, and facilitates electrolytes ion transfer.