One of unsolved puzzles about water lies in how ion-water interplay affects its freezing point. Here, we report the direct link between tetrahedral entropy and the freezing behavior of water in Zn -based electrolytes by analyzing experimental spectra and molecular simulation results. A higher tetrahedral entropy leads to lower freezing point, and the freezing temperature is directly related to the entropy value. By tailoring the entropy of water using different anions, we develop an ultralow temperature aqueous polyaniline| |Zn battery that exhibits a high capacity (74.17 mAh g ) at 1 A g and -80 °C with ~85% capacity retention after 1200 cycles due to the high electrolyte ionic conductivity (1.12 mS cm ). Moreover, an improved cycling life is achieved with ~100% capacity retention after 5000 cycles at -70 °C. The fabricated battery delivers appreciably enhanced performance in terms of frost resistance and stability. This work serves to provide guidance for the design of ultralow temperature aqueous batteries by precisely tuning the water structure within electrolytes.