Silicon-based anodes can increase the energy density of Li-ion batteries (LIBs) owing to their large weights and volumetric capacities. However, repeated charging and discharging can rapidly deteriorate the electrochemical properties because of a large volume change in the electrode. In this study, a commercial Fe-Si powder was coated with Al2O3 layers of different thicknesses via atomic layer deposition (ALD) to prevent the volume expansion of Si and suppress the formation of crack-induced solid electrolyte interfaces. The Al2O3 content was controlled by adjusting the trimethyl aluminum exposure time, and higher Al2O3 contents significantly improved the electrochemical properties. In 300 cycles, the capacity retention rate of a pouch full-cell containing the fabricated anodes increased from 69.8% to 72.3% and 79.1% depending on the Al2O3 content. The powder characterization and coin and pouch cell cycle evaluation results confirmed the formation of an Al2O3 layer on the powder surface. Furthermore, the expansion rate observed during the charging/discharging of the pouch cell indicated that the deposited layer suppressed the powder expansion and improved the cell stability. Thus, the performance of an LIB containing Si-alloy anodes can be improved by coating an ALD-synthesized protective Al2O3 layer.