In this paper, Li4Ti5O12 (LTO) hollow microspheres with the shell consisting of nanosheets have been synthesized via a hydrothermal route and following calcination. Because of the favorable transport properties of this hollow structure, it is the rate performance at high current densities which is exceptional. When the LTO hollow microspheres were used as the anode material in lithium ion battery, they exhibited superior rate performance and high capacity even at a very high rate (131mAhg−1 at 50C).