Zinc anode suffers from tough issues such as dendrite, corrosion, and hydrogen evolution, which lead to premature battery failure and thus restrict the practical application of aqueous zinc-metal batteries (ZMABs). Herein, a polydentate-ligand tactic is introduced to reconstruct solvation structure, improve corrosion resistance, and trigger selective dendrite-free deposition via β-Alanyl-L-histidine (AH). With abundant amino, amide, carboxyl, and imidazolyl groups, AH shows a chelation effect, which partially substitutes solvated SO42− and enters the Zn2+ solvation sheath to facilitate desolvation. Those groups also increase the strong H-bond proportion of electrolyte, stabilizing water and suppressing corrosion and hydrogen evolution reactions. Moreover, with multisite coordination, the AH preferentially adsorbs on Zn(002) to induce a stable functional C, N, O, and S-rich solid-electrolyte interphase with zincophilic and hydrophobic properties. It homogenizes both the electric field and concentration field and guides preferential Zn growth along (002), realizing stable and dendrite-free Zn anode. As a result, the obtained Zn anode with AH electrolyte exhibits a high CE of 99.28%, extended stability of over 6000 h, and a long lifespan of over 1000 cycles for Zn//MnO2 batteries. This work offers a novel design strategy of additive toward stabilization of Zn anodes for practical ZMABs.