Vertically oriented, highly ordered TiO2 nanotube arrays were fabricated via electrochemical anodization of high purity Ti sheet and Ti foil, which is increasing importance due to their impressing properties in a variety of applications including dye-sensitized solar cells, hydrogen generation by water photoelectrolysis, potocatalysis, and gas sensor. The well aligned TiO2 nanotube arrays by potentiostatic anodization of Ti foil (with 0.3mm thickness) were constructed. We have achieved the self-aligned high ordered nanotube arrays in aqueous electrolyte containing HF and ethylene glycol electrolyte containing NH4F. Depending on the fluoride ion mobile velocity, the resulting nanotubes arrays exhibit the different morphology. The elaborated electrolyte on the morphology of the self-organized nanotubes arrays was investigated. Thermal annealing on the anodized Ti induced crystalline formation, which is confirmed by Raman spectroscopy measurement.