Temperature is a state variable that significantly affects thermodynamic and kinetic performances and performance degradation of energy storage materials. In this Perspective, we address our recent progress in the energy storage performance and transporting phenomena of supercapacitors when temperatures are elevated to >100 °C. Electrodes include reduced graphene oxide film and foam and conductive metal organic frameworks; electrolytes include phosphoric-acid-doped polybenzimidazole and double networked ionogels. The electrochemical, thermal, and mechanical properties of electrodes and electrolytes are correlated with energy storage performance and degradation at high temperatures. We also address the fundamental understanding of ion transport of polymeric electrolytes and the emergence of nanoscale-confined fast mobile protons at elevated temperatures.