As potential high-performance anode materials for Li-ion batteries (LIBs), mesoporous TiNb2O7 (M-TNO) microspheres were synthesized through a facial solvothermal and subsequent calcination process. Due to the reduced charge and ion transfer distances, the M-TNO samples showed smaller charge transfer resistance and faster Li ion diffusion. The void space in the M-TNO can boast the structural stability by buffer the volume change during cycling to result in long cycle life. A high specific capacity of 319 mA h g−1 can be realized in the first cycle at 0.1 C, and the cyclability and kinetics were superior at the electrode in the following cycles. The M-NTO presented outstanding high rate performances at 1 C and 10 C, with a high rate capacity of 155 mA h g−1 and a very slow capacity fading of 0.03% per cycle after 500 cycles at 10 C. Electrochemical measurements indicating that the elevated rate capacity and long cycle life were derived from the more proportion of capacitive capacity, smaller charge transfer resistance and faster Li+ ion diffusion.