TiO2-coated SnO2 (TCS) hollow spheres, which are new anode materials for lithium ion (Li-ion) batteries, were prepared and characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV), and galvanostatic charge/discharge tests. The results obtained from XRD, SEM, and TEM show that TiO2 can be uniformly coated on the surface of SnO2 hollow spheres with the assistance of anionic surfactant. The cyclic voltammograms indicate that both TiO2 and SnO2 exhibit the activity for Li-ion storage. The charge/discharge tests show that the prepared TCS hollow spheres have a higher reversible coulomb efficiency and a better cycling stability than the uncoated SnO2 hollow spheres.