High-energy density lithium ion batteries (LIBs) rely heavily on innovations of electrode materials. Herein, the porous TiNb2O7/carbon nanofibers (TNO/CNFs) have been prepared through the hydrothermal method and electrostatic spinning method as the anode for the Li-ion battery. The structure of porous TNO/CNFs after annealing at 700 °C for 2 h is intact, and lots of holes are found on that surface of nanofibers. Porous TNO/CNFs as the anode show better electrochemical performance than TNO/CNFs, the capacity retention of porous TNO/CNFs is 81.6% (147 mA h/g) with an exceptionally high rate (at 20 C rate). And the capacity retention of porous TNO/CNFs is higher than ≈77% that of TNO/CNFs (112 mA h/g). The superior electrochemical performance of these porous TNO/CNFs can be attributed to the unique porous carbon nanofiber structure: this structure of porous nanofibers not only provides a larger effective area for contact with the electrolyte but also reduces the rate-limiting Li diffusion path, leading to faster charge transfer.