A facile solvothermal treatment without any template is employed to synthesize TiO2 mesoporous microspheres with nanorod structure. The post-calcination of the microsphere sample at 500°C with carbon source leads to the formation of C-coated TiO2 with the same structure. All of the prepared samples have been characterized by the techniques of X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Additionally, N2 adsorption-desorption isotherm curves have been depicted to show the tunable mesopores and high specific surface area of the prepared pure and C-coated TiO2. A growth scheme is also proposed to elucidate the formation process of the mesoporous microspheres with nanorods on the surface. The electrochemical results show that both of the prepared samples have better electrochemical performance than commercial anatase TiO2 due to the nanorod and mesoporous structures, which provides direct and open channals for efficient Li+ ion diffusion. Moreover, the prepared C-coated TiO2 has superior rate property and cycling performance with specific capacity of 157.4mAhg−1 at 1C rate even after 200 cycles. The galvanostatic charge-discharge voltage indicates that the C-coated TiO2 with improved electronic conductivity has the broadest voltage platform comparable to Li4Ti5O12. Therefore, the C-coated TiO2 with mesoporous microspheres and nanorod structure can be an attractive candidate as functional anode materials.