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The NC/CL-20 composite fibers were successfully prepared using electrospinning method. The composite fibers have potential application in propellant, pyrotechnics and explosives by modifying the mass ratio of CL-20 in the composite fibers. The weight percentage of NC in the precursor solution was from 8% to 24%, and a mixture of acetone and N, N-dimethyl formamide was used as the solvent. In order to get uniform and smooth fibers with CL-20 homogeneously dispersed, the maximum content of CL-20 should be less than 75% in the fibers. The diameter of the fibers was from nanoscale to several micrometers. Thermal decomposition properties of the composite fibers were also characterized by DSC.