The invention discloses a nano-porous Al-Ni-M-RE-R amorphous alloy used as a hydrogen evolution catalytic electrode, wherein a transition metal element M is Fe, Co, Cr and Cu, a rare earth element REis Y, La, Gd and Ce, a precious metal R is Pt, Ru, Pd, Rh, Au and Ir, and a hydrogen evolution catalytic electrode comprises the following components in percentage by mass: Al, 2-12% of Ni, 1-13% of M, 2-13% of RE, and 0.2-7% of R, and is treated by adopting a constant current method, a corrosion method or a pulse corrosion current method, so that the prepared nano porous amorphous alloy is stablein structure, large in specific surface area, adjustable in component, structure and morphology and high in catalytic activity. According to the invention, when the nano-porous amorphous alloy hydrogen evolution electrode is used as a water electrolysis hydrogen evolution catalytic electrode, the hydrogen evolution overpotential is 40-65 mV and the Tafel slope is 10-60 mV / dec under the current density of 10 mA.cm<-2>, so that the nano-porous amorphous alloy hydrogen evolution electrode has excellent hydrogen evolution catalytic activity.