Nest-like TiO2 hollow microspheres composed of nanowires have been successfully synthesized via a simple process including hydrothermal treatment and calcination. The hydrothermal treatment time plays important roles in the morphologies and crystallographic structures for the final products. The obtained nest-like TiO2 hollow microspheres gives a reversible capacity of 228mAhg−1 at 0.5C rate. Furthermore, the nest-like TiO2 hollow microspheres could possess relatively high reversible capacities even at higher charge/discharge rates. The reversible capacities of approximately 210, 191, 166, 150 and 130mAhg−1 are obtained at 1C, 2C, 5C, 10C and 20C, respectively. The superior electrochemical performance of hollow TiO2 microspheres composed of nanowires is mainly related to its efficient hierarchical nanostructures.