In order to improve the dispersibility and energy output of nano-boron powder， n-B/NC/F₂₆₀₂ core-shell nanofibers were prepared by coaxial electrospinning method. The morphology of the samples prepared with different core solution mass fraction， shell solution mass fraction， working voltage， distance from needle to collector and injection rate were analyzed by scanning electron microscope（SEM）， and the optimum preparation conditions were explored. Scanning electron microscope （SEM）， X-ray photoelectron spectrometer（XPS） and infrared spectrometer （IR） were used to analyze the morphology of the samples prepared under the best preparation conditions. The combustion performance test， thermodynamic simulation and DSC-TG were used to analyze the combustion performance. The results show that the optimum preparation conditions is 15% of the core layer solution， shell solution mass fraction 15%， working voltage 16 kV， distance between needle and collector 12 cm， core flow rate 3.6 mL·h^-1， shell flow rate 6 mL·h^-1. The average diameter of the spinning product was 1.32 μm. The combustion performance test shows that the highest peak of combustion pressure is 0.51 MPa， and the average pressure boost rate is 0.61 MPa·s^-1， showing excellent combustion performance. Thermodynamic simulation showed that the average molecular weight of the product was 29 g·mo^-1， and the combustion was sufficient. DSC-TG showed that the weight gain of boron in n-B/NC/F₂₆₀₂ was 43.43% more than that of the original boron powder， and the peak exothermic temperature of boron in n-B/NC/F₂₆₀₂ was 41 ℃ lower than that of the original boron powder. The coaxial electrospinning method could better optimize the nanostructure of the fibers.