Aqueous Zn-ion batteries represent a promising platform for grid-scale energy storage, yet the advancement is constrained by persistent interfacial challenges on dendrite growth and parasitic corrosion. Herein, a novel strategy leveraging the multidentate coordination of Zn²⁺ and solvent molecules is introduced to synergistically tailor the solvation sheath and modulate the interfacial mass-charge conduction. Reconfiguring the inherent H-bond network and interfacial chemistry effectively suppresses side reactions and ensures uniform Zn deposition. Consequently, a Zn||Zn battery delivers an exceptional cumulative plating capacity of 23.0 Ah·cm^–2 and operates steadily for over 4600 h under harsh conditions of 10 mA·cm^–2. When coupled with an I₂ cathode, the full battery retains excellent durability across 65,000 cycles at 10 A·g^–1, with an ultralow capacity decay of 0.0004% per cycle. A practical pouch battery delivers 11.5 mAh and maintains 90.0% capacity after 130 cycles. Multiscale spectroscopy and computations elucidate ligand exchange within the solvation sheath and the synergy with a dynamic interfacial adsorption layer, establishing a green and efficient molecular strategy for stabilizing Zn electrochemistry.