TiO2 nanotubes arrays were prepared by anodization of Ti in EG containing H3PO4 and NH4F electrolyte. The samples were characterized by X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Energy dispersive X-ray spectroscopy (EDX) and photoluminescence spectra (PL). The as-anodized TiO2 nanotubes were annealed in inert (argon), reducing (nitrogen), or oxidizing (oxygen) atmosphere at 400 °C for 4 hr. XRD analysis revealed that the TiO2 nanotubes were anatase after annealing. In this study, the TiO2 nanotubes annealed in argon exhibited the highest degradation rate of methyl orange (MO) solution under ultraviolet irradiation among the samples. The degradation rate was approximately 98% after 5h, which may be ascribed to the large amount of oxygen vacancies and defects (phosphorus) within the Ar - TiO2 sample that simultaneously increased the degradation rate of MO.