Titania nanotube arrays were fabricated in deionize water and glycerol mixed electrolyte containing a certain amount of NH4F. Three different polishing methods were used for pretreatment of Ti substrates: polished by hand with abrasive paper, by polishing machine, or by chemical polishing fluid (HF:HNO3=1:4, in volumetric ratio). The morphology of three different samples were imaged by scanning electron microscopy, and their photoelectrical properties were studied as well. Experimental results showed that Titania nanotube arrays grown on the Ti substrate and polished by polishing fluid has highly-ordered and well-defined nanotube structure. The effects of anodization potential and duration on synthesis of highly-ordered TiO2 nanotubes were also studied in this paper. Both the layer thickness and nanotube diameter linearly increase with the increasing potential. The layer thickness also increases with prolongation of anodization time. By optimizing the preparation conditions, we can successfully control the geometrical structure of TiO2 nanotube arrays with diameters in the range between 50 and 200 nm and the layer thickness between 800 and 2000 nm.