Antimony-carbon-graphene fibrous composites were prepared by the electrospinning/spray process as freestanding anodes for sodium-ion batteries. Antimony nanoparticles distribute in conductive carbonized polymer fibers and graphene flakes. The unique structure prevents the aggregation of the antimony nanoparticles and buffers the mechanical stress from volume change of antimony during repeated alloying/de-alloying process. The composites demonstrated an excellent electrochemical performance as anode material for sodium-ion batteries, with a reversible capacity of 274mAh/g after 100 charge-discharge cycles at a current density of 100mA/g.