TiO 2 is well‐known nanomaterials and mostly used as solid nanoparticles, and normal hollow spheres for photocatalysts or electrode materials. In this study, a novel self‐templated method is presented to successfully fabricate high‐surface‐area ultrathin nanosheets constructed TiO 2 hollow spheres through the solvothermal treatment of the titanate–silicone composite particles combined with calcination. The uniquely structured hollow spheres exhibit excellent rate capability and good cycle stability even at a high current density of ≈10 C for the anode material of Li‐ion battery.