Al86Fe10Zr4 amorphous ribbons were prepared by melt spinning. The amorphous characteristics and crystallization behavior of the amorphous ribbons was investigated by means of X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The results show that the as-spun ribbons are in fully amorphous state. The DSC trace reveals that two-step crystallization occurs in the amorphous ribbon during the heating scanning, and the onset temperatures of the first and the second crystallization are about 603 and 718 K, respectively. The activation energies for the two-step crystallization are 273 and 239 kJ/mol, respectively. Furthermore, the effect of crystallization on the electrochemical properties was examined. The results indicate that the partially crystallized ribbon exhibits better corrosion resistance than that of the fully amorphous ribbon, while the fully crystallization deteriorates the corrosion resistance of the amorphous ribbon.