Polystyrene (PS)/SnO2 core-shell microspheres were prepared with alkoxide as precursor and hollow SnO2 spheres were fabricated by a subsequent calcination process. The influence of the concentration of precursor and the size of the PS templates on morphologies and properties of the microspheres was investigated by transmission electron microscope, field emission scanning electron microscope observation, and Brunauer-Emmett-Teller measurements. X-ray diffraction and Fourier transform infrared analysis revealed the microspheres were composed of SnO2 nanocrystals. As anode material, hollow SnO2 microspheres were assembled into lithium-ion batteries and displayed high activity. (c) 2007 The Electrochemical Society.