Hollow spherical Li4Ti5O12 was prepared by the macroemulsion method. Its frameworks were built by many nano-Li4Ti5O12 particles. This hollow spherical material shows an excellent electrochemical performance, and can be charged-discharged at 20C (3.4 A g(-1)) with the specific capacity of 95 mAh g(-1). Besides its excellent rate capability, this material also has a good capacity retention; over 500 cycles charge and discharge at 2C, the specific capacity stays very stable at the value of 140 mAh g(-1) with a loss of only 0.01% per cycle. The excellent electrochemical performance of hollow spherical Li4Ti5O12 is mainly due to its stable hollow structure and nanoscale particles. (C) 2008 The Electrochemical Society.