Hierarchical layered hydrous lithium titanate and Li4Ti5O12 microspheres assembled by nanosheets have been successfully synthesized via a hydrothermal process and subsequent thermal treatment. The electrochemical properties of the two samples have been investigated by galvanostatic methods. The former, with the obvious layered structure and a large surface area, delivers a reversible capacity of 180mAhg−1 after 200 cycles at 200mAg−1. As for Li4Ti5O12, with the intriguing and unique sawtooth-like morphology, it presents exceptional high rate performance and excellent cycling stability. Up to 132mAhg−1 is obtained after 200 cycles at 10,000mAg−1 (57C), proving itself promising for high-rate applications.