Thermal stability, structural evolution and corrosion resistance of melt spun Al86Ni10Zr4 amorphous alloy under different annealing treatment conditions were investigated via differential scanning calorimetry (DSC), X-ray diffractometry (XRD), transmission electron microscopy (TEM) and electrochemical tests. It is shown that the Al86Ni10Zr4 amorphous alloy has a large crystallization zone width and can remain amorphous for a long time at room temperature without crystallization and has high thermal stability. Structural characterization and properties analysis showed that the nano-sized α-Al phase precipitated on the amorphous matrix after annealing at 523 K improved the corrosion resistance of the ribbon, which is due to the fact that the corrosion resistance depends not only on the homogeneous amorphous structure but also on the content of oxides in the surface passivation film.