The work aims to increase the surface area and improve the hydrogen evolution properties of Fe82Nb6B12 ribbons. Fe82Nb6B12 ribbons were prepared by vacuum quenching device and α-Fe from nanocrystal/amorphous biphasic structure was obtained by controlling the speed of the copper roller. With the corrosion difference of α-Fe nanocrystal/amorphous biphasic structure in 0.5 mol/L sulfuric acid, the amorphous nanoporous was fabricated by dealloying method. The effects of copper roll speed and dealloying time on phase, composition, morphology and hydrogen evolution performance of the samples were investigated with X-ray diffractometer (XRD), scanning electron microscope (SEM), differential scanning calorimetry (DSC) and electrochemical method. The 1 kr/min sample was almost fully crystallized. α-Fe nanocrystal /amorphous duplex alloy was successfully prepared at 2~3 kr/min. The content of α-Fe nanocrystals in the ribbon decreased with the increase of the copper roller speed. After dealloying, the amorphous nanoporous structure was successfully prepared. The larger the rotation speed of the copper roller was, the smaller the pore diameter and the smaller the specific surface area were. The 4 kr/min sample was amorphous, and no porous structure was observed after alloying. The 2 kr/min sample with porous structures exhibited the best hydrogen evolution performance, which delivered a current density of 10 mA/cm2 at overpotential of 220 mV with Tafel slope of 105 mV/dec. In general, the Fe82Nb6B12 alloy with α-Fe nanocrystal/amorphous dual-phase structure can be prepared through melt-spinning. By selective etching of α-Fe nanocrystals, an amorphous porous structure can be obtained, and the specific surface area of the ribbon is significantly increased, thereby improving the hydrogen evolution performance.