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Owing to zinc dendrites and parasitic reactions, aqueous Zn‐metal batteries often suffer from poor reversibility and cyclability. Electrolyte additives present a promising strategy to improve Zn anode stability. However, the ever‐evolving perspectives and mechanisms, paradoxically, complicate battery design, causing a scenario where any electrolyte additive seems to be effective. Herein, it is taken ionic liquid (IL) additives as an example and detailed explored the impact of three typical IL anions, namely OTF−, TFA−, and BF4−. It is identified that the primary determinant of electrolyte additives as their electrical double layer (EDL) structures and their subsequent solid‐electrolyte interface (SEI) composition. An advantageous EDL structure, akin to an ion‐shield, can reduce the absorption of H2O molecules, which further enrich the SEI with zincophilic and hydrophobic components, thereby mitigating parasitic reactions and Zn dendrite formation. As a result, the Zn||Zn cell with optimal [EMIM]OTF additives demonstrates an exceptional cycling life under challenging conditions, its cumulative plated capacity surpasses most previously reported results by utilizing different IL additives. This work extends beyond performance enhancements, representing a valuable exploration of key criteria for electrolyte additives is believed. These insights are expected to offer fundamental guidance for future research and electrolyte design. [ABSTRACT FROM AUTHOR]