We report the formation and extraordinary Li-storage properties of TiO2 hollow nanofibers by co-axial electrospinning in both the half-cell and full-cell configurations. Li-insertion properties are first evaluated as anodes in the half-cell configuration (Li/TiO2 hollow nanofibers) and we found that reversible insertion of ~0.45 moles is feasible at a current density of 100 mA g(-1). The half-cell displayed a good cyclability and retained 84% of its initial reversible capacity after 300 galvanostatic cycles. The full-cell is fabricated with a commercially available olivine phase LiFePO4 cathode under optimized mass loading. The LiFePO4/TiO2 hollow nanofiber cell delivered a reversible capacity of 103 mA h g(-1) at a current density of 100 mA g(-1) with an operating potential of ~1.4 V. Excellent cyclability is noted for the full-cell configuration, irrespective of the applied current densities, and it retained 88% of reversible capacity after 300 cycles in ambient conditions at a current density of 100 mA g(-1).