Hierarchical assembly of hollow microstructures is of great scientificity and practical value. In this paper, a hydrothermal synthesis of Li4Ti5O12 hollow microspheres assembled by nanosheets is introduced. Transmission electron microscopy (TEM) image shows that such Li4Ti5O12 microspheres, with sizes of 2μm in diameter, are composed of a hollow inner cavity and thin outer shell assembled by nanosheets. A possible growth mechanism of the structure is further expounded. The Li4Ti5O12 hollow microspheres calcinated at 700°C display extremely good electrochemical performance, including high capacity (147.3mAhg−1 at 3C), excellent cyclic stability (95.0% capacity retention after 100 cycles at 3C) and remarkable rate capability (131.3mAhg−1 at 20C).