Na3V2(PO4)(3)/C nanofibers are prepared by a pre-reduction assisted electrospinning method. In order to maintain the perfect fibrous architecture of the Na3V2(PO4)(3)/C samples after calcining, a series of heat treatment parameters are studied in detail. It is found that the heat treatment process shows important influence on the morphology and electrochemical performance of Na3V2(PO4)(3)/C composite nanofibers. Under the calcining conditions of 800 degrees C for 10 h with a heating rate of 2.5 degrees C min(-1), the well-crystallized uniform Na3V2(PO4)(3)/C nanofibers with excellent electrochemical performances are successfully obtained. The initial discharge specific capacities of the nanofibers at 0.05, 1, and 10C are 114.0, 106.0, and 77.9 mAh g(-1), respectively. The capacity retention still remains 97.0% after 100 cycles at 0.05C. This smooth, uniform, and continuous Na3V2(PO4)(3)/C composite nanofibers prepared by simple electrospinning method, is expected to be a superior cathode material for sodium-ion batteries.