A highly ordered TiO2 nanotube array on Ti substrate was fabricated by using an electrochemical anodic oxidation method. The morphology, crystalline phase, and photoelectrochemical property of the nanotube array were characterized. The photocatalytic activity of the nanotube array was evaluated by the decolorization of methyl orange in aqueous solution using the different light sources. The effects of structure and morphology of the nanotube array on its photocatalytic activity were investigated. It was found that the photoabsorption behavior of the TiO2 nanotube film depended on the structures of the nanotube array. The nanotube array films exhibited a drastically enhanced photocurrent, and a higher photocatalytic activity compared with the TiO2 nanoparticle film prepared by the regular sol-gel method. The experimental results indicated that the film thickness markedly influenced the photocatalytic activity of nanotube array film, and the 2.5 microm-thick TiO2 nanotube array film appeared a maximum photodegradation efficiency to methyl orange. However, for a given nanotube length, the tube diameter was only very slightly affected the photocatalytic efficiency in this work. The explanation for some critical structure factors of TiO2 nanotube array in the photocatalytic activity was discussed as well.