Sodium ion batteries have a huge potential for large-scale energy storage for the low cost and abundance of sodium resources. In this work, a novel structure of ultrafine polycrystalline TiO2 nanofibers is prepared on nickel foam/carbon cloth by a simple vapor deposition method. The as-prepared TiO2 nanofibers show excellent performance when used as anodes for sodium-ion batteries. Specifically, the TiO2 nanofibers@nickel foam electrode delivers a high reversible capacity of 263.2 mAh g−1 at 0.2 C and maintains a considerable capacity of 144.2 mAh g−1 at 10 C. The TiO2 nanofibers@carbon cloth electrode also shows excellent high-rate capability, sustaining a capacity of 148 mAh g−1 after 2000 cycles at 10 C. It is believed that the novel nanofibrous structure increases the contact area with the electrolyte and greatly shortens the sodium ion diffusion distance, and meanwhile, the polycrystalline nature of nanofibers exposes more intercalation sites for sodium storage. Furthermore, the density functional theory calculations exhibit strong ionic interactions between the exposed TiO2 (101) facets and sodium ions, leading to a preferable sodiation/desodiation process. The unique structural features endow the TiO2 nanofibers electrodes great advantages in rapid sodium storage with an outstanding high-rate capability.