Antimony-based materials have become promising anodes within lithium-ion batteries (LIBs) due to their low cost and the high theoretical capacity. However, there is a potential to further enhance the electrochemical performance of such antimony-based materials. Herein, Sb2Se3@C nanofibers (Sb2Se3@CNFs) are designed and obtained via a novel electrospinning method. Upon electrochemically testing as an anode within LIBs, the Sb2Se3@CNFs (annealed at 600 °C) delivers a remarkably good cycling performance of 625 mAh/g at 100 mA/g after 100 cycles. Moreover, it still remains at 490 mAh/g after 500 cycles with an applied current density of 1.0 A/g. The excellent performance of the Sb2Se3@CNFs can be attributed to the fact that the N-doped C matrices not only remit the volume expansion of materials, but also enhance the electrical and ionic conductivity thusly increasing the lithium-ion diffusion. The obtained Sb2Se3@CNFs are promising anode for LIBs in the future.