Structure relaxation and crystallization of Al 83 Ni 10 Ce 7 metallic glass were studied by different scanning calorimetry (DSC) and X-ray diffraction (XRD). According to the DSC scan, it is interesting to find that the second exothermic peak changes with pre-annealing temperatures (below glass transition temperature), suggesting a change in the amorphous structure upon relaxation. Continuous heating crystallization and isothermal crystallization exhibit different crystallization mechanism of the present alloy. fcc-Al and a metastable phase precipitate simultaneously in the first stage crystallization during continuous heating; however, only a metastable phase precipitates during isothermal annealing below glass transition temperature (T g ).