While the rechargeable aqueous zinc-ion batteries (AZIBs) have been recognized as one of the most viable batteries for scale-up application, the instability on Zn anode–electrolyte interface bottleneck the further development dramatically. Herein, we utilize the amino acid glycine (Gly) as an electrolyte additive to stabilize the Zn anode–electrolyte interface. The unique interfacial chemistry is facilitated by the synergistic “anchor-capture” effect of polar groups in Gly molecule, manifested by simultaneously coupling the amino to anchor on the surface of Zn anode and the carboxyl to capture Zn2+ in the local region. As such, this robust anode–electrolyte interface inhibits the disordered migration of Zn2+, and effectively suppresses both side reactions and dendrite growth. The reversibility of Zn anode achieves a significant improvement with an average Coulombic efficiency of 99.22% at 1 mA cm−2 and 0.5 mAh cm−2 over 500 cycles. Even at a high Zn utilization rate (depth of discharge, DODZn) of 68%, a steady cycle life up to 200 h is obtained for ultrathin Zn foils (20 μm). The superior rate capability and long-term cycle stability of Zn–MnO2 full cells further prove the effectiveness of Gly in stabilizing Zn anode. This work sheds light on additive designing from the specific roles of polar groups for AZIBs.