Hollow TiO2 microspheres are designed from an Ostwald ripening process, then as-synthesized hollow TiO2 spheres are used as a template to synthesize Li4Ti5O12 via a simple hydrothermal synthesis method. Such microspheres display good electrochemical performance, including high capacity, excellent cyclic stability and remarkable rate capability. The hollow Li4Ti5O12 microspheres calcined at 700 degrees C display extremely good electrochemical performance, including high capacity (174.6 mAh/g at 1C rate), excellent cyclic stability (97.7% capacity retention after 50 cycles at 1C rate) and remarkable rate capability (140.3 mAh/g at 15 C-rate).