In this work, titanium dioxide nanotubes were prepared by using titanium foils via electrochemical anodization in ethylene glycol solutions containing different amounts of water and fluoride in the ranges of 1%–3% and 0.15%–0.5%, respectively, to determine their effects on morphology, optical, and crystalline structure properties. Annealing processes were performed on all samples in the range between 273 and 723 K. Morphology and structure properties of the samples were studied by scanning electron microscopy, X-ray diffraction (XRD), and transmission electron microscopy. Titanium dioxide (TiO₂) nanotubes, through anodization method, are strongly influenced by conditions, like fluoride concentration and applied voltages. Tube lengths between 2 and 7 μm were obtained, exhibiting different diameters and wall thicknesses. When alternating voltage was applied, the outer surface of the nanotubes exhibited evenly spaced ring-shaped regions, while smooth tubes were observed when constant voltage was applied. Reflection peaks, corresponding to Brookite, Anatase, and Rutile, of TiO₂ phases, were observed from the XRD pattern. These phases were corroborated via μXRD measurements, and the Ti₃O₅ phase was also observed in detail. Absorption coefficient (α), optical band gap (Eg), and extinction coefficient (ε) of TiO₂ nanotubes were calculated by transmittance spectra in the UV–Vis range. Strong absorption was noted in the UV region from reflectance and absorbance measurements. A correlation between synthesis parameters and physical properties is presented.