Sb-C nanofibers are synthesized successfully through a single-nozzle electrospinning technique and subsequent calcination. The structural and morphological characterizations reveal the uniform nanofiber structure with the Sb nanoparticles embedded homogeneously in the carbon nanofibers. Electrochemical experiments show that the Sb-C nanofiber electrode can deliver large reversible capacity (631 mA h g(-1)) at C/15, greatly improved rate capability (337 mA h g(-1) at 5 C) and excellent cycling stability (90% capacity retention after 400 cycles). The superior electrochemical performances of the Sb-C nanofibers are due to the unique nanofiber structure and uniform distribution of Sb nanoparticles in carbon matrix, which provides a conductive and buffering matrix for effective release of mechanical stress caused by Na ion insertion/extraction and prevent the aggregation of the Sb nanoparticles.