<p>Aqueous zinc-iodine batteries (AZIBs) hold great promise for grid-scale energy storage; however, their long-term cycling stability is severely compromised by zinc anode instability and the adverse polyiodide shuttle effect. In this study, we developed a tri-functional sulfonated electrolyte-separator system by incorporating ethyldiglycol acetate (CA), 2-sulfobenzoic acid monoammonium (SAM), and an electrospun sulfonated poly (ether ether ketone) (ESP) separator. This integrated system synergistically enhances the reversibility of AZIBs by expanding the operational temperature range, promoting solid electrolyte interphase (SEI) formation, and spatially confining polyiodide species. Specifically, SAM and CA collaboratively modulate the hydrogen bond network while simultaneously facilitating SEI formation, thereby significantly improving electrochemical reversibility. The ether/ester groups in CA modify the Zn²⁺ solvation sheath and disrupt H-bonding, thereby suppressing water decomposition, mitigating water-related side reactions, and extending the operational temperature range. Moreover, SAM preferentially adsorbs onto Zn through electrostatic interactions and subsequently decomposes to form an S/N-containing SEI, which facilitates Zn²⁺ deposition along (002) plane and suppresses dendrites. Significantly, SAM and the ESP separator work synergistically to construct a sulfonate-rich environment, enabling a dynamic spatial confinement effect on polyiodides via continuous electrostatic repulsion by sulfonate groups, thereby enhancing iodine utilization efficiency. This triple-regulation strategy provides a promising approach for achieving high Coulombic efficiency and long cycling stability in AZIBs over a wide temperature range.</p>