1D branched TiO nanomaterials play a significant role in efficient photocatalysis and high-performance lithium ion batteries. In contrast to the typical methods which generally have to employ epitaxial growth, the direct in situ growth of hierarchically branched TiO nanofibers by a combination of the electrospinning technique and the alkali-hydrothermal process is presented in this work. Such the branched nanofibers exhibit improvement in terms of photocatalytic hydrogen evolution (0.41 mmol g h ), in comparison to the conventional TiO nanofibers (0.11 mmol g h ) and P25 (0.082 mmol g h ). Furthermore, these nanofibers also deliver higher lithium specific capacity at different current densities, and the specific capacity at the rate of 2 C is as high as 201. 0 mAh g , roughly two times higher than that of the pristine TiO nanofibers.