Despite notable progress in thermoelectric (TE) materials and devices, developing TE aerogels with high-temperature resistance, superior TE performance and excellent elasticity to enable self-powered high-temperature monitoring/warning in industrial and wearable applications remains a great challenge. Herein, a highly elastic, flame-retardant and high-temperature-resistant TE aerogel, made of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/single-walled carbon nanotube (PEDOT:PSS/SWCNT) composites, has been fabricated, displaying attractive compression-induced power factor enhancement. The as-fabricated sensors with the aerogel can achieve accurately pressure stimuli detection and wide temperature range monitoring. Subsequently, a flexible TE generator is assembled, consisting of 25 aerogels connected in series, capable of delivering a maximum output power of 400 μW when subjected to a temperature difference of 300 K. This demonstrates its outstanding high-temperature heat harvesting capability and promising application prospects for real-time temperature monitoring on industrial high-temperature pipelines. Moreover, the designed self-powered wearable sensing glove can realize precise wide-range temperature detection, high-temperature warning and accurate recognition of human hand gestures. The aerogel-based intelligent wearable sensing system developed for firefighters demonstrates the desired self-powered and highly sensitive high-temperature fire warning capability. Benefitting from these desirable properties, the elastic and high-temperature-resistant aerogels present various promising applications including self-powered high-temperature monitoring, industrial overheat warning, waste heat energy recycling and even wearable healthcare.