Fluororubber/glycidyl azide polymer/hexanitrohexaazaisowurtzitane （F₂₆₀₂/GAP/CL-20） composite fibers were prepared through electrospinning process， and the effects of solution concentration， binder ratio， spinning voltage and injection rate on the morphology were explored. Scanning electron microscope （SEM） was used to observe the morphology of composite fibers prepared under different conditions. It is found that when the solution concentration is 20%， the binder F₂₆₀₂/GAP content is 10%， the spinning voltage is 14 kV， and the injection rate is 5×10^-3 L·h^-1， the F₂₆₀₂/GAP/CL-20 composite fiber exhibits a three-dimensional network structure and its surface is uniform and smooth. X-ray diffraction （XRD）， infrared spectroscopy （IR）， differential scanning calorimeter （DSC） and mechanical sensitivity tests were performed on the F₂₆₀₂/GAP/CL-20 composite fiber and raw CL-20. The results show that the crystal form of CL-20 in the composite fiber changes from ε to β after electrospinning. There is no chemical reaction between CL-20 and F₂₆₀₂/GAP during the electrospinning process. After electrospinning， the apparent activation energy of F₂₆₀₂/GAP/CL-20 increases from 178 kJ·mol^-1 of the raw CL-20 to 374.3 kJ·mol^-1， indicating that the composite possesses better thermal stability. The impact sensitivity H₅₀ increases from 21.2 cm to 62.6 cm， and the friction sensitivity decreases from 84% to 52%. Therefore， the effect of sensitivity reduction is significant.