We synthesized polycrystalline Ti2Nb10O29 nanofibers (NFs) via a simple post-annealing process of as-electrospun polymeric NFs as an anode material for Li-ion batteries (LIBs). During the first discharge/charge process, the Ti2Nb10O29 NFs annealed at 900°C exhibited insertion/extraction capacities of up to 344 and 304mAhg−1, corresponding to 19.1 and 16.7mol Li+ per formula unit, respectively. This material exhibited excellent rate capability (93mAhg−1 at 15Ag−1) and a higher average diffusion coefficient (DLi =∼1.5×10−12 cm2 s−1) than Ti2Nb10O29 powder (∼6.9×10−13 cm2 s−1). This performance can be attributed to the unique nanostructure of firmly interconnected, highly crystalline Ti2Nb10O29 nano-grains, which facilitates the Li+ and electron transport. The kinetics obtained from current-voltage curves indicate a mixture of diffusion-limited and capacitive processes. The suggested electro-spinning/post annealing approach can effectively provide a simple route towards high-quality Ti2Nb10O29 NF-based anodes for high-performance LIBs.