Antimony doped SnO2 (ATO) microspheres composed of ATO nanoparticles were prepared by using a hydrothermal process in a nonaqueous and template-free solution from the inorganic precursors (SnCl4 and Sb(OC2H5)3). The physical properties of the as-synthesized samples were investigated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption–desorption isotherms, and X-ray photoelectron spectrum (XPS). The resulting particles were highly crystalline ATO microspheres in the diameter range of 3–10μm and with many pores. The as-prepared samples were used as negative materials for lithium-ion battery, whose charge–discharge properties, cyclic voltammetry, and cycle performance were examined. The results showed that a high initial discharge capacity of 1981mAhg−1 and a charge capacity of 957mAhg−1 in a potential range of 0.005–3.0V was achieved, which suggests that tin oxide-based materials work as high capacity anodes for lithium-ion rechargeable batteries. The cycle performance is improved because the conducting ATO nanoparticles can also perform as a better matrix for lithium-ion battery anode.