communication stations of switching 5G signal are inevitable. In that case, supercapacitors that can work at high temperatures must be explored to expand the application range and improve equipment security. However, studies on the development of high-temperature supercapacitors are few because of several challenges, such as: poor cycling stability of the electrode material at high temperature and low boiling point of the electrolyte. [11][12][13] Therefore, supercapacitors operating at high temperatures impose strict requirements on materials and electrolytes.Carbon-based supercapacitors have elicited extensive attention because of their rapid charge/discharge rate, high electrical conductivity, and good thermostability. [14][15][16][17][18][19][20] Extensive effort has been exerted to obtain high-temperature, carbon-based supercapacitors with improved the performance. For example, Yury et al. reported on wide range of temperature supercapacitors based on active carbon (AC). By adjusting the size and shape of AC, the double-layer capacitors could be operated in a wide range of temperature from −100 to 60 °C. [21] Bao et al. reported an all-solid-state planar with activated graphene as the cathode; the planar showed excellent electrochemical performance and safety at 80 °C. [22] However, the cycling stability was unsatisfactory, and the inherent low energy density of pure carbon resulted in a limited application. Motivated by this challenging issue, researchers have conducted studies to improve the electrochemical property. Recent research has shown that the doping of nitrogen (N), boron (B), phosphorus (P), sulfur (S), and fluorine (F) heteroatoms in carbon frame can improve the stability and energy density of carbon materials. [23][24][25][26][27] For example, Feng et al. reported graphene aerogels with N and B doping; the aerogels showed an enhanced energy density of 8.65 W h kg −1 and improved cycling stability close to 100% after 1000 cycles. [28] Our previous work also proved that the introduction of B and N can alter the electrostatic attraction of materials, thereby expanding the operating voltage window to 4.8 V and resulting in a high energy density of 200 Wh kg −1 . [29] Furthermore, the inserted B and N in C lattice structures can effectively improve the charge density and activate the C electron around B and N. [30] Carbon nanomaterials have elicited much research interest in the energy storage field, but most of them cannot be used at high temperatures. Thus, a supercapacitor with high energy and desired stability at high temperatures is urgently required. Herein, BCN nanotubes (BCNNTs) with excellent performance at high temperatures are generated on carbon fibers by optimizing the ratio of B and N. The nanotubes' morphology can effectively alleviate the structural damage caused by the rapid adsorption/ desorption of the electrolyte during long-time charge/discharge cycles at high temperatures, thus improving the high-temperature cycle stability. The symmetric supercapacitors that are assembled with...