Silver vanadates (SVOs) have been widely investigated as cathode materials for high-performance lithium-ion batteries (LIBs). However, similar to most vanadium-based materials, SVOs suffer from structural collapse/amorphization and vanadium dissolution from the electrode into the electrolyte during the Li insertion and extraction process, causing poor electrochemical performance in LIBs. We employ ultrathin Al₂O₃ coatings to modify β-AgVO₃ (as a typical example of SVOs) by an atomic layer deposition (ALD) technique. The galvanostatic charge-discharge test reveals that ALD Al₂O₃ coatings with different thicknesses greatly affected the cycling performance. Especially, the β-AgVO₃ electrode with ~10 nm Al₂O₃ coating (100 ALD cycles) exhibits a high specific capacity of 271 mAh g⁻¹, and capacity retention is 31%, much higher than the uncoated one of 10% after 100 cycles. The Coulombic efficiency is improved from 89.8% for the pristine β-AgVO₃ to 98.2% for Al₂O₃-coated one. Postcycling analysis by cyclic voltammetry (CV), cyclic voltammetry (EIS), and scanning electron microscopy (SEM) disclose that 10-nm Al₂O₃ coating greatly reduces cathode-electrolyte interphase (CEI) resistance and the charge transfer resistance in the β-AgVO₃ electrode. Al₂O₃ coating by the ALD method is a promising technique to construct artificial CEI and stabilize the structure of SVOs, providing new insights for vanadium-based electrodes and their energy storage devices.