The photocatalytic activity of TiO2 based nanotube (TNT) and nanofiber (TNF) coatings has been investigated, in correlation to their structure, morphology, specific surface area, acidity and the amount of surface H2O molecules and -OH groups. Characterization of these materials was carried out using grazing incidence X-ray diffraction (GIXRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFT). The photocatalytic activity has been quantified by two different methods, based on the photodegradation of methylene blue (the pattern of water-soluble organic pollutant) and acetone (the pattern of volatile organic pollutant), respectively. Results of our investigations revealed that TNF coatings were significantly more active in case of both photodegradation processes in air and water, as compared to TNT, even if the specific surface area of TNF films was smaller than the adequate surface area of TNT. The microstructure of produced materials, the amount of adsorbed -OH groups and H2O molecules located on the surface of materials, and the acidity of the surface, were the main factors which affect their photoactivity. Photocatalytic properties of tubular and porous TiO2-based materials are the resultant of the compilation of individual factors impact and any of them cannot be neglected. (C) 2016 Elsevier B.V. All rights reserved.