Flower-like TiO2 hierarchical structures were synthesized by a solvothermal strategy using tetrabutyl titanate as the titanium source. The obtained flower-like TiO2 hierarchical structures were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), specific surface area analysis, Raman spectroscopy and energy-dispersive spectroscopy (EDS). Results show that the flower-like hierarchical structures are composed of anatase titanium dioxide. TiO2 nanowires are first formed by the self-assembly of nanocrystals with a diameter of 20 nm, and then several TiO2 nanowires produce a petal-like structure. Finally, flower-like TiO2 hierarchical structures with a diameter of 2 ~ 2.3 μm are assembled by these petal-like structures. The electrochemical properties of the flower-like TiO2 hierarchical structures were studied by using these hierarchical structures as the anode material in a lithium-ion battery. The flower-like TiO2 hierarchical structures have an initial discharge capacity of 473.9 mAh/g at a current density of 100 mA/g and an initial discharge capacity of 244.4 mAh/g at a current density of 2 A/g in the potential range of 0.01~3 V. The photocatalytic properties of the flower-like TiO2 hierarchical structures were studied by degrading methyl orange (MO) solution under ultraviolet (UV) light irradiation. When used as a photocatalyst, the degradation rate of MO is 95.8% after 40 min of UV irradiation, showing that the flower-like TiO2 hierarchical structures have excellent photocatalytic activity.