Wearable sensors for high temperatures (WSHT) applications pose a significant challenge in the electronics field due to the inherent inability of most electronics to function in harsh environments. Triboelectric nanogenerators (TENG) present a substantial potential for applications in such challenging conditions. Herein, a fully-recyclable flame-retardant triboelectric elastomer is developed, which exhibits superior charge stability under high temperature conditions and proposes the specially designed synergistic fillers that play a dual role by trapping more charges into the interface and stabilizing the char layers via layer-ball-layer structure. An efficient flame-retardant system is presented, which exhibits a 31% lower fire growth index than the individual components. The maximum surface charge density of this triboelectric elastomer can reach 361 µC m−2, while this surface charge density can be preserved to 70.9% after 16 s of combustion (≈520 °C) and to 37.9% by continuously working at 130 °C. At last, utilizing this flame-retardant triboelectric elastomer, smart firemen's boots featuring gait analysis for identification and second level early warning systems have been developed. This work paves the way for the development of triboelectric materials and intelligent wearable devices suitable for applications in harsh environments.