Mesoporous hollow TiO2 microspheres with controlled size and hierarchical nanostructures are designed from a process employing in suit template-assisted and hydrothermal methods. The results show that the hollow microspheres composed of mesoporous nanospheres possess very stable reversible capacity of 184mAhg−1 at 0.25C and exhibit extremely high power of 122mAhg−1 at the high rate of 10C. The superior high-rate and high-capacity performance of the sample is attributed to the efficient hierarchical nanostructures. The hollow structure could shorten the diffusion length for lithium ion in the microspheres. The large mesoporous channels between the mesoporous nanospheres provide an easily-accessed system which facilitates electrolyte transportation and lithium ion diffusion within the electrode materials. The electrolyte, flooding the mesoporous channels, can also lead to a high electrolyte/electrode contact area, facilitating transport of lithium ions across the electrolyte/electrode interface. The small mesopores in the meosporous nanospheres can make the electrolyte and lithium ion further diffuse into the interior of electrode materials and increase electrolyte/electrode contact area. The small nanoparticles can also ensure high reversible capacity.