Aqueous batteries hold great promise for safe, sustainable energy storage, but their operation at low temperatures is limited by electrolyte freezing that impedes bulk ion transport and by sluggish cation desolvation at the electrode interface. Herein, we report a high-entropy hydrogel electrolyte (HEE) that leverages polymeric complexity to enhance ion conduction and interfacial desolvation at low temperatures, enabling aqueous battery operation down to -80 °C. The increased mixing entropy from various polymer-water interactions disrupts the ordered water network, suppressing ice formation with preserved ion-conducting pathways at low temperatures. Concurrently, the enhanced solvation entropy generates varying ion coordination environments with loosely bound solvation shells, promoting desolvation and stabilizing the solid-electrolyte interphase. As a proof of concept, the HEE achieves highly reversible zinc (Zn) plating/stripping with an average Coulombic efficiency of 99.7%, exhibits stable cycling for over 4000 h, and supports aqueous Zn-based battery operation even at -80 °C. This entropy-engineering strategy offers an effective route for realizing energy storage under extreme conditions.