Application of degradable organic electronics based on biomaterials, such as polylactic‐co‐glycolic acid and polylactide (PLA), is severely limited by their low thermal stability. Here, a highly thermally stable organic transistor is demonstrated by applying a three‐arm stereocomplex PLA (tascPLA) as dielectric and substrate materials. The resulting flexible transistors are stable up to 200 °C, while devices based on traditional PLA are damaged at 100 °C. Furthermore, charge‐ trapping effect induced by polar groups of the dielectric is also utilized to significantly enhance the temperature sensitivity of the electronic devices. Skin‐like temperature sensor array is successfully demonstrated based on such transistors, which also exhibited good biocompatibility in cytotoxicity measurement. By presenting combined advantages of transparency, flexibility, thermal stability, temperature sensitivity, degradability, and biocompatibility, these organic transistors thus possess a broad applicability such as environment friendly electronics, implantable medical devices, and artificial skin.

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