Flame-retardant negative tribo-materials are desirable for triboelectric nanogenerators (TENGs) using under harsh conditions, such as thermal power fields and aerospace. The existed negative tribo-materials are mainly polymeric materials, and their high-temperature stability and fire resistance still need to be improved. Herein, poly(p-phenylene benzobisoxazole) aerogels (PBOAs) were used as the negative tribo-materials in TENGs. Because of the large porosity and high specific surface area, the resultant TENGs exhibit maximum open circuit voltage, short-circuit current density and charge density of 40 V, 2.9 mA m−2 and 72 μC m−2, respectively. The device can light 36 LED bulbs and charge the capacitor to 10 V within 250 s. The device can also be used as a self-powered, highly sensitive sensor for monitoring human motion and even slight collisions with an impulse of only 3 μN s. PBOA has been paired with aluminum foil to fabricate PBOA/Al TENGs, which exhibit V OC of 32 V, J SC of 1.2 mA m−2 and charge density of 32 μC m−2 at a temperature as high as 350 °C, demonstrating the possibility of application of TENGs in high-temperature environments.