The nitrocellulose(NC) nano-fibers were prepared by means of electrostatic spinning. The composition of spinning solvent systems used in the preparation was determined with optimized condition. Results show that the nitrocellulose nano-fibers with diameter of 80 nm can be obtained when the mixed liquid composed of acetone and ethanol is in the volume ratio of 1:1, and spinning voltage14 kV, spinning concentration 9%, spinning fluid flow 0.1 mL·h^-1 and received distance 22 cm. The electrostatic spinning does not change the molecular chain structure of nitrocellulose. The decomposition heat of nitrocellulose nano-fibers is 1835.80 J·g^-1 which is higher than that of traditional nitrocellulose.