The sustained water consumption and uncontrollable dendrite growth strongly hamper the practical applications of rechargeable zinc (Zn) metal batteries (ZMBs). Herein, for the first time, we demonstrate that trace amount of chelate ligand additive can serve as a “molecular sieve-like” interfacial barrier and achieve highly efficient Zn plating/stripping. As verified by theoretical modeling and experimental investigations, the benzenesulfonic acid groups on the additive molecular not only facilitates its water solubility and selective adsorption on the Zn anode, but also effectively accelerates the de-solvation kinetics of Zn2+. Meanwhile, the central porphyrin ring on the chelate ligand effectively expels free water molecules from Zn2+ via chemical binding against hydrogen evolution, and reversibly releases the captured Zn2+ to endow a dendrite-free Zn deposition. By virtue of this non-consumable additive, high average Zn plating/stripping efficiency of 99.7% over 2100 cycles together with extended lifespan and suppressed water decomposition in the Zn||MnO2 full battery were achieved, thus opening a new avenue for developing highly durable ZMBs.