Syntheses of Al-based metastable alloys from powder mixtures of elemental Al and amorphous Fe78Si12B10 [x at. % Al + (100 — x) at. % (Fe78Si12B10)] alloy by mechanical milling (MM) using a planetary ball mill are investigated. X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) are used to characterize their structure during the MM process. For the powder mixture with low content of Al (x = 75, 82), fully amorphous material can be obtained by MM, while for the milled product with a high content of Al (x = 90), nanocrystalline Al and amorphous phases are obtained. During the initial milling stage, the Al atoms are dissolved into the amorphous Fe78Si12B10 matrix by heavy deformation. Consequently, the Al-enriched homogeneous amorphous alloys are produced with the disappearance or shrinkage of diffraction peaks of Al in the XRD pattern. Further milling of the powder mixture with 75 at. % Al results in the crystallization of amorphous phase and the formation of nanocrystalline Al3Fe type phase. The crystallization products of all as-milled samples are very similar, composed of Al13Fe4 and AlFe3 phases. It is suggested that the kinetics of nucleation and growth favor the formation of amorphous phase due to the existence of amorphous phase initially. The amorphization reaction by mechanical milling is diffusion process, but defects and strain also play an important role.