The composite nanofibers of Aluminium nanoparticles (AlNPs) and nitrocellulose (NC) have been successfully fabricated by electrospinning, the fibers with potential applications in the propellant combined good mechanical properties of the fibers and high burning rates of AlNPs. SEM images indicated that the distilled water played an important role in formation of nanofibers. The morphology and diameters of AlNPs/NC nanofibers were strongly influenced by the solution concentrations and electrostatic field strength. By optimizing the distilled water content, solution concentrations and electrostatic field strength, the smooth AlNPs/NC nanofibers were prepared. TEM images showed that AlNPs distributed uniformly into the composite nanofibers.