LAUSR

Rechargeable aqueous zinc batteries are promising in next‐generation sustainable energy storage. However, the low zinc (Zn) metal anode reversibility and utilization in aqueous electrolytes due to Zn corrosion and poor Zn2+ deposition kinetics significantly hinder the development of Zn‐ion batteries. Here, a dual salt/dual solvent electrolyte composed of Zn(BF4)2/Zn(Ac)2 in water/TEGDME (tetraethylene glycol dimethyl ether) solvents to achieve reversible Zn anode at an ultrahigh depth of discharge (DOD) is developed. An “inner co‐salt and outer co‐solvent” synergistic effect in this unique dual salt/dual solvent system is revealed. Experimental results and theoretical calculations provide evidence that the ether co‐solvent inhibits water activity by forming hydrogen bonding with the water and coordination effects with the proton in the outer Zn2+ solvation structure. Meanwhile, the anion of zinc acetate co‐salt enters the inner Zn2+ solvation structure, thereby accelerating the desolvation kinetics. Strikingly, based on the electrolyte design, the zinc anode shows high reversibility at an ultrahigh utilization of 60% DOD with 99.80% Coulombic efficiency and 9.39 mAh cm−2 high capacity. The results far exceed the performance reported in electrolyte design work recently. The work provides fundamental insights into inner co‐salt and outer co‐solvent synergistic regulation in multifunctional electrolytes for reversible aqueous metal‐ion batteries.