TiO2 thin films and TiO2 nanotube arrays were fabricated on Si and quartz substrates by atomic layer deposition (ALD) with the application of anodic aluminum oxide (AAO) template at 400°C. In particular, the thickness of the film and the wall thickness of the nanotubes can be controlled precisely using ALD technique. The photoluminescence (PL) characteristic of TiO2 thin films was improved with increased thickness. However, for TiO2 nanotube arrays, with the decrease of the wall thickness, higher PL intensity was obtained. Compared TiO2 thin film with TiO2 nanotube arrays, TiO2 nanotube arrays exhibited a better performance on PL characteristic due to larger surface area. Owing to larger amount of oxygen vacancies on the surface, compared with the volume factor, surface area was a more important factor that affected the performance of PL characteristics. Therefore, when the volume of TiO2 nanotube arrays became smaller, the ratio of surface area to volume was increased and the influence from the surface area became the dominating factor on the performance of the PL characteristics.