Alkaline Al-air batteries (AABs) are gaining increasing attention for large-scale energy storage systems due to their attractive intrinsic safety and cost-effectiveness. Nonetheless, the future development of AABs is substantially hampered by water-induced self-corrosion processes on the Al anode. In this work, we introduce an amino acid derivative, namely Nα-Boc-N1-formyl-L-tryptophan (NBLT), into a 4 M NaOH electrolyte to construct a unique layer that can effectively regulate the surface microstructure of the Al anode. The findings of the experiments show that NBLT can be used as a reliable corrosion inhibitor. The effectiveness of such inhibitors increases with NBLT concentration, reaching a maximum of 73.9% at 1.5 mM. In comparison to the pristine condition, there is a significant increase in anode utilization from 31.8% to 82.9%, capacity density from 947.9 to 2469.1 mA h g-1, and energy density from 1261.6 to 3384.6 W h kg-1. Theoretical calculations indicate that the carboxyl moieties present in the NBLT molecule establish coordination bonds with the Al atoms, thereby exerting a dominant role in the formation of the self-assembled barrier. The present investigation paves an effective strategy to inhibit reactions between anodes and electrolytes for advanced AABs.