Searching for free-standing and cost-efficient hydrogen evolution reaction (HER) electrocatalysts with high efficiency and excellent durability remains a great challenge for the hydrogen-based energy industry.Here,we report fabrication of a unique hierarchically porous structure,i.e.,nanoporous Ni (NPN)/metallic glass (MG) composite,through surface dealloying of the specially designed Ni40Zr40Ti20 MG wire.This porous composite is composed of micrometer slits staggered with nanometer pores,which not only enlarges effective surface areas for the catalytic reaction,but also facilitates the release of H2 gas.As a result,the NPN/MG hybrid electrode exhibited the prominent HER performance with a low overpotential of 78 mV at 10 mAcm-2 and Tafel slope of 42.4 mV dec-1,along with outstanding stability in alkaline solutions.Outstanding catalytic properties,combining with their free-standing capability and cost efficiency,make the current composite electrode viable for HER applications.