Herein, we report a simple base-free hydrothermal route for the synthesis of mesoporous TiO2 fibers by using chitosan as direct agent. This hierarchical structure combines advantages of mesopores constructed by interconnected sub-10nm nanocrystals on nanoscale and 1D structure with large aspect ratio on micron-scale, which is desired structural characteristic needed for the high-performance anode materials. Benefiting from such unique structural features, it demonstrates superior high charge/discharge capability, good cycling stability and rate capability when used as lithium-ion batteries electrode. For example, it can deliver a capacity of 174mAhg−1 at 0.5C and 137mAhg−1 at 5C after 100 cycles.