A critical current challenge in the development of proton pseudocapacitors is developing antifreezing electrolytes and high-performance proton storage materials in extreme environments. Here, we design an antifreezing proton pseudocapacitor using a high-concentration phosphoric acid electrolyte and pseudocapacitive electrode materials, which delivers an outstanding rate capacity and cycle life below − 40 °C. Comprehensive physical characterization techniques and theoretical simulations demonstrate that the solvation structure of the electrolyte defines the freezing point and electrochemical stability window, which is crucial for achieving fast charge carrier mobility and avoiding side effects. The pseudocapacitive hydrated tungsten oxide anodes and Prussian blue analogue cathodes with their open crystal structures achieve fast proton transport and storage, resulting in excellent electrochemical performance from − 60 to 25 °C (1000 cycles with no capacity fading at − 40 °C). Benefiting from the synergistic effect between the electrolyte and electrode materials, the fabricated proton pseudocapacitors exhibit remarkable low-temperature electrochemical performance. It achieves a maximum energy density of 39 Wh kg−1 and a broadened electrochemical window from 1.7 V at 25 °C to 2.3 V at − 60 °C. This work provides a comprehensive strategy to develop high-performance proton energy storage devices under ultralow-temperature conditions.