A Sn-SnO2/C nanocomposite was synthesized using the electrospinning method. Thermal analysis was used to determine the content range of Sn and SnO2 in the composite. The composite was characterized by X-ray diffraction, and the particle size and shape in the Sn-SnO2/C composite were determined by scanning and transmission electron microscopy. The results show that the Sn-SnO2/C composite takes on a nanofiber morphology, with the diameters of the nanofibers distributed from 50 to 200 nm. The electrochemical properties of the Sn-SnO2/C composite were also investigated. The Sn-SnO2/C composite as an electrode material has both higher reversible capacity (887 mAh·g−1) and good cycling performance in lithium-anode cells working at room temperature in a 3.0 V to 0.01 V potential window. The Sn-SnO2/C composite could retain a discharge capacity of 546 mAh/g after 30 cycles. The outstanding electrochemical properties of the Sn-SnO2/C composite obtained by this method make it possible for this composite to be used as a promising anode material.