In this work, TiO2 3D nanostructures (TF30) were prepared via a facile wet chemical process using ammonium hexafluorotitanate. The synthesized 3D TiO2 nanostructures exhibited well-defined crystalline and hierarchical structures assembled from TiO2 nanorods with different thicknesses and diameters, which comprised numerous small beads. Moreover, the maximum specific surface area of TiO2 3D nanostructures was observed to be 191 m2g-1, with concentration of F ions on the surface being 2 at%. The TiO2 3D nanostructures were tested as photocatalysts under UV irradiation using Rhodamine B solution in order to determine their photocatalytic performance. The TiO2 3D nanostructures showed a higher photocatalytic activity than that of the other TiO2 samples, which was likely associated with the combined effects of a high crystallinity, unique features of the hierarchical structure, a high specific surface area, and the advantage of adsorbing F ions.