Hierarchical TiO2-based hollow spheres were successfully synthesized via a hydrothermal method using FeSO4 center dot 7H(2)O, CoSO4 center dot 7H(2)O and ZnSO4 center dot 7H(2)O as soft templates. The as-prepared hollow spheres are well dispersed with the diameters of 2-4 mu m. The shell and the interior surface of the spheres are composed of loosely packed grains, which provide a large specific surface area to facilitate lithium-ion diffusion processes. Among the three types of hybrid hollow spheres, TiO2/Fe2O3 shows the highest reversible capacity and best cycling stability (discharge capacities of 290.8 and 210.5 mAh/g were achieved after 100 cycles at 0.1C and 1C, respectively) and rate performance (from 461.1 mAh/g at 0.1C to 79.3 mAh/g at 5C with recovery to 288.6 mAh/g at 0.1C) for anode materials in lithium-ion batteries.