Herein, the preparation of nanotubular and porous TiO2 structures (TNS) is presented for photocatalytic applications. Different TNS were prepared in three different types of glycerol- and ethylene glycol-based electrolytes on a large area (approx. 20 cm2) via anodization using different conditions (applied potential, fluoride concentration). Morphology, structure, and optical properties of TNS were characterized by Scanning Electron Microscopy (SEM), X-ray Diffractometry (XRD), and Diffuse Reflectance Spectroscopy (DRS), respectively. All TNS possess optical band-gap energy (EBG) in the range from 3.1 eV to 3.2 eV. Photocatalytic degradation of caffeine was conducted to evaluate the efficiency of TNS. Overall, nanotubular TiO2 possessed enhanced degradation efficiencies (up to 50% degradation) compared to those of porous TiO2 (up to 30% degradation). This is due to the unique properties of nanotubular TiO2, e.g., improved incident light utilization. As the anodization of large areas is, nowadays, becoming a trend, we show that both nanotubular and porous TiO2 are promising for their use in photocatalysis and could be potentially applicable in photoreactors for wastewater treatment. We believe this present work can be the foundation for future development of efficient TiO2 nanostructures for industrial applications.