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The raised demand for portable electronics in high-temperature environments (>150 °C) stimulates the search for solutions to release the temperature constraints of power supply. All-solid-state microsupercapacitors (MSCs) are envisioned as promising on-chip power supply components, but at present, nearly none of them can work at temperature over 200 °C, mainly restricted by the electrolytes which possess either low thermal stability or incompatible fabrication process with on-chip integration. In this work, we have developed a novel process to fabricate highly thermally stable ionic liquid/ceramic composite electrolytes for on-chip integrated MSCs. Remarkably, the electrolytes enable MSCs with graphene-based electrodes to operate at temperatures as high as 250 °C with a high areal capacitance (~72 mF cm−2 at 5 mV s−1) and good cycling stability (70 % capacitance retention after 1000 cycles at 1.4 mA cm−2).