Despite their cost-effectiveness and intrinsic safety, aqueous zinc-ion batteries have faced challenges with poor reversibility originating from various active water-induced side reactions. After systematically scrutinizing the effects of water on the evolution of solvation structures, electrolyte properties, and electrochemical performances through experimental and theoretical approaches, a hydrated deep eutectic electrolyte with a water-deficient solvation structure ([Zn(H2O)2(eg)2(otf)2]) and reduced free water content in the bulk solution is proposed in this work. This electrolyte can dramatically suppress water-induced side reactions and provide high Zn2+ mass transfer kinetics, resulting in highly reversible Zn anodes (∼99.6% Coulombic efficiency over 1000 cycles and stable cycling over 4500 h) and high capacity Zn//NVO full cells (436 mA h g−1). This work will aid the understanding of electrolyte solvation structure–electrolyte property–electrochemical performance relationships of aqueous electrolytes in aqueous zinc-ion batteries
