Abstract: Crystalline alloys were obtained by isothermal annealing on the basis of the DSC of Zr₆₀Al₁₅Ni₂₅、Zr_52.5Al₁₀Ni₁₀Cu₁₅Be_12.5 and Zr₆₅Al₁₀Ni₁₀Cu₁₅ bulk metallic glasses.The analysis of polarization curves of BMGs and its crystalline states,combining SEM and EDS observation,SEM and EDS indicated that in 0.5mol/L H₂SO₄,both the BMGs and their crystalline alloys have a very good corrosion resistance.Compared with crystalline alloys,the BMGs have a better performance,it is due to the lack of grain boundaries,dislocations and other defects,and the higher active elements in the BMGs,the faster the alloys to passive state.