Spinel lithium titanate, Li4Ti5O12, with novel hollow-sphere structure was fabricated by a sol–gel process using carbon sphere as template. The effect of the hollow-sphere structure as well as the wall thickness on the Li storage capability and high rate performance was electrochemically evaluated. High specific capacity, especially better high rate performance was achieved with this Li4Ti5O12 hollow-sphere electrode material with thin wall thickness. It is believed that this macroporous hollow-sphere structure has shortened the Li diffusion distance, increased the contact area between Li4Ti5O12 and electrolyte, and also led to better mixing of the active material with AB. All these factors have resulted in the good rate capability of the hollow-sphere structured Li4Ti5O12 electrode material.