Triboelectric nanogenerator (TENG) can convert tiny mechanical energy into precious electrical energy. Constant improvements to the output performance of TENG is not only the driving force for its sustainable development, but also the key to expand its practical applicability in modern smart devices. However, most previous studies were conducted at room temperature, ignoring the influence of temperature on the output performance of TENG. Additionally, due to thermionic emission effect, the electrons transferred to a dielectric surface can be released into a vacuum after contact electrification. Therefore, TENG cannot maintain an effective electrical output under high-temperature conditions. Here, a series of high-temperature operatable flexible TENGs (HO-TENGs) based on nanofiber/microsphere hybrid membranes (FSHMs) was fabricated by electrospinning and electrospraying. The V_oc of HO-TENG is 212 V, which is 2.33 times higher than that of control TENG. After 10,000 cycle stability tests, the HO-TENG shows excellent durability. Especially, this HO-TENG can maintain 77% electrical output at 70 °C compared to room temperature, showing excellent high-temperature operability. This study can not only provide a reference for the construction of advanced high-performance TENG, but also provide a certain experimental basis for efficient collection of mechanical energy in high-temperature environment and promote the application of TENG devices in harsh environments.