The reversibility and long‐term cycling stability of aqueous zinc‐ion batteries (AZIBs) in a wide temperature range have rarely been explored. Herein, diethylene glycol monoethyl ether (DG) is introduced as an electrolyte additive to enhance Zn performance within a wide temperature range of −35 to 65 °C. Operando synchrotron Fourier transform infrared spectroscopy analysis combined with molecular dynamics simulations reveal that the introduction of DG disrupts the initial hydrogen bonding network of the aqueous electrolyte, restructuring the solvation structure surrounding Zn²⁺ ions and mitigating water‐induced parasitic reactions. Adding DG reduces the freezing point of the aqueous electrolyte without compromising its incombustibility. Moreover, operando electrochemical quartz crystal microbalance with dissipation monitoring (EQCM‐D) and X‐ray photoelectron spectroscopy demonstrated that the coordinated DG and OTF⁻ undergo reductive decomposition, forming a self‐healing solid electrolyte interphase comprising an inorganic/organic ZnF₂‐ZnS, which can effectively suppress the notorious side reactions and guide the uniform Zn deposition. Consequently, the symmetric Zn/Zn cells demonstrate excellent cycling stability for 3500 h under 1 mA cm⁻² at 25 °C, and for 1000 h under 1 mA cm⁻² at both −35 and 65 °C. Full batteries with a DG‐containing electrolyte exhibit a long lifespan of 5000 cycles at 2 A g⁻¹.