Based on the conversion and alloying reactions, antimony sulfide (Sb2S3) with a theoretical discharge specific capacity of 946 mAh g−1 is a hopeful anode material for lithium/sodium ion batteries. Nevertheless, the poor electronic conductivity of Sb2S3 and the serious volume expansion during alloying reaction bring about the rapid capacity fading, which severely hinder its practical application. The design of morphology/structure and/or combining with carbon materials is the common strategies to address these issues. Herein, a simple electrospinning technology coupled with hydrothermal reaction is employed to synthesize the Sb2S3/carbon-silicon oxide (Sb2S3/CS) nanofibers for the first time. The obtained Sb2S3/CS nanofibers show superior lithium/sodium storage properties. Specifically, the Sb2S3/CS electrode maintains a high discharge specific capacity of 566 mAh g−1 under 200 mA g−1 after 200 cycles in lithium-ion batteries. For sodium storage, the Sb2S3/CS electrode obtains a discharge specific capacity of 321 mAh g−1 under 200 mA g−1 over 200 cycles. One-dimensional Sb2S3/CS nanofibers with good electronic conductivity accelerate the transport of ions and electrons, and effectively buffer the volume change of Sb2S3 nanoparticles during electrochemical reaction process, bringing about the excellent electrochemical properties.