Nanometal fuels have a great potential in energetic field for their high reactivity and their low ignition temperature. However, their high surface energy makes them aggregate. In this work, the electrospinning was employed to fabricate the nanoboron/nitrocellulose nanofibers expecting to enhance the reactivity of nanoboron. The results of SEM and TEM show that nanoboron is well dispersed in the nitrocellulose fiber matrix. TG-DSC confirms that the nanoboron in the fibers reacted more drastically than pure nanoboron and nanoboron/nitrocellulose powders resulted from the thermal analysis. Combustion propagation velocity shows that the presence of nanoboron in nitrocellulose fibers causes the faster and more intensive burning than the mechanical mixture of nanoboron and nitrocellulose.