Hierarchical Sb₂S₃ hollow microspheres assembled by nanowires have been successfully synthesized by a simple and practical hydrothermal reaction. The possible formation process of this architecture was investigated by X-ray diffraction, focused-ion beam-scanning electron microscopy dual-beam system, and transmission electron microscopy. When used as the anode material for lithium-ion batteries, Sb₂S₃ hollow microspheres manifest excellent rate property and enhanced lithium-storage capability and can deliver a discharge capacity of 674 mAh g⁻¹ at a current density of 200 mA g⁻¹ after 50 cycles. Even at a high current density of 5000 mA g⁻¹, a discharge capacity of 541 mAh g⁻¹ is achieved. Sb₂S₃ hollow microspheres also display a prominent sodium-storage capacity and maintain a reversible discharge capacity of 384 mAh g⁻¹ at a current density of 200 mA g⁻¹ after 50 cycles. The remarkable lithium/sodium-storage property may be attributed to the synergetic effect of its nanometer size and three-dimensional hierarchical architecture, and the outstanding stability property is attributed to the sufficient interior void space, which can buffer the volume expansion.