The zinc (Zn) metal electrode suffers from poor stability especially at high currents and large capacities due to insufficient Zn²⁺ supply and intricate side reactions. Despite significant progress, the fundamental understanding of the correlation between anions and the induced electrode/electrolyte interface remains elusive. Here, a comparative framework based on anion-polarity hybridization is constructed, generating variations of regulation in the bulk solvation and interfacial structure. Herein, a dual-anion electrolyte towards the durable Zn electrode is modulated by incorporating the strong-polarity acetate anion (Ac⁻) together with the trifluoromethanesulfonate anion (OTf⁻), which synchronously prompts anion enrichment in the solvation structure and abundant Zn²⁺ aggregation in the Helmholtz layer. Remarkably, a cumulative plating capacity of 15.25 A h cm⁻² (3050 h) is harvested in the Zn‖Zn symmetric cell at 10 mA cm⁻² and 10 mA h cm⁻². Moreover, the designed electrolyte demonstrates superior adaptability to varying low temperatures and high temperature (60 °C). Zn-ion hybrid capacitors and Zn–air batteries also manifest enhanced electrochemical performance, demonstrating the feasibility of dual-anion chemistry in various electrochemical devices. This study provides the fundamental principle to construct advanced electrolytes via anion chemistry for high-performance Zn-based electrochemical devices.