Highly ordered TiO2 nanotube array (TN) films were prepared by anodization of titanium foil in a mixed electrolyte solution of glycerin and NH4F and then annealed at 200°C, 400°C, 600°C, and 800°C, respectively. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), water contact angle (WCA), and photoluminescence (PL). It was found that low temperature (below 600°C) has no significant influence on surface morphology, but the diameter of the nanotube increases from 40 to 50 nm with increasing temperature. At 800°C, the nanotube arrays are completely destroyed and only dense rutile film is observed. Samples unannealed and annealed at 200°C are amorphous. At 400°C, anatase phase appears. At 600°C, rutile phase appears. At 800°C, anatase phase changes into rutile phase completely. The wettability of the TN films shows that the WCAs for all samples freshly annealed at different temperatures are about 0°. After the annealed samples have been stored in air for 1 month, the WCAs increase to 130°, 133°, 135°, 141°, and 77°, respectively. Upon ultraviolet (UV) irradiation, they exhibit a significant transition from hydrophobicity to hydrophilicity. Especially, samples unannealed and annealed at 400°C show high photoinduced hydrophilicity.