This paper reports the microstructure and electrochemical properties of Si-Al-Fe ternary amorphous alloys prepared by rapid solidification as an anode for lithium secondary batteries. The microstructure was analyzed using XRD and HR-TEM with EDS mapping. In accordance with DSC analysis, annealing was performed to crystallize the active nano-Si in the amorphous alloy. Thus, nano-Si forms (~80 nm) embedded in the matrix alloy, such as Fe₂Al₃Si₃, FeSi₂, and Fe_0.42Si_2.67, were successfully synthesized. The electrode based on the Si-Al-Fe ternary alloy delivered an initial discharge capacity of approximately 700 mAh ^g-1, and exhibited a high Coulombic efficiency of 99.0~99.6% from the 2^nd to 70^th cycles.