Hierarchical structured Li4Ti5O12, assembling from randomly oriented nanosheets with a thickness of about 10–16nm, is fabricated by a facile hydrothermal route and following calcination. It is demonstrated that the as-prepared sample has good cycle stability and excellent high rate performance. In particular, the discharge capacity of 128mAhg−1 can be obtained at the high current density of 2000mAg−1, which is about 87% of that at the low current density of 200mAg−1 upon cycling, indicating that the as-prepared sample can endure great changes of various discharge current densities to retain a good stability. In addition, the pseudocapacitive effect based on the hierarchical structure, also contributes to the high rate capability of Li4Ti5O12, which can be confirmed in cyclic voltammograms.