Achieving a power supply for robots operating at high temperatures or in combustion environments is crucial for human life. As an emerging energy collection technique, triboelectric nanogenerators (TENGs) possess great sustainability, however, their electrical output performances rapidly deteriorate due to the failure of polymer based triboelectric layers in harsh environments. Herein, an outstanding high-temperature resistant and electrically stable TENG is fabricated using composites of polyphenylene benzodiazole (PBO) fiber enhanced liquid crystal polyarylate (LCP). The intrinsic inert PBO fibers are modified by aminated naphthalimide sizing to effectively improve the interfacial interactions of PBO/LCP composites in terms of high tensile strength (409.3 MPa) and storage modulus at 250 °C (0.18 GPa). More importantly, besides good flexibility, high heat resistance index of 303.9°C, and impressive limiting oxygen index of 36.4%, the resultant TENGs showed enhanced electrical output performance at elevated temperature. The output voltage reached 42 V at 200°C, which could drive a louder buzzer compared to the reduced voltages (by 26.5%) at room temperature. Even after burning on the flame for 10 s, the output voltage is almost 100% retained. The findings demonstrate the great potential of interface molecular engineering and structure-function integrated composites for the wearable electronics of robots in extreme environments.