One-dimensional carbon nanofibers with highly dispersed tin (Sn) and tin antimonide (SnSb) nanoparticles are prepared by electrospinning in the presence of antimony-doped tin oxide (denoted as ATO) wet gel as the precursor. The effect of ATO dosage on the microstructure and electrochemical properties of the as-fabricated Sn-SnSb/C composite nanofibers is investigated. Results indicate that ATO wet gel as the precursor can effectively improve the dispersion of Sn nanoparticles in carbon fiber and prevent them from segregation during the electrospinning and subsequent calcination processes. The as-prepared Sn-SnSb/C nanofibers as the anode materials for lithium-ion batteries exhibit high reversible capacity and stable cycle performance. Particularly, the electrode made from Sn-SnSb/C composite nanofibers obtained with 0.9 g of ATO gel has a high specific capacity of 779 mAh·g−1 and 378 mAh·g−1 at the current density of 50 mA·g−1 and 5 A·g−1, respectively, and it exhibits a capacity retention of 97% after 1200 cycles under the current density of 1 A·g−1. This is because the carbon nanofibers can form a continuous conductive network to buffer the volume change of the electrodes while Sn and Sn-SnSb nanoparticles uniformly distributed in the carbon nanofibers are free of segregation, thereby contributing to electrochemical performances of the electrodes.