Series of nanosized anion-containing TiO2-base materials with anatase-type structure were synthesized from N, Cl-containing precursors using two preparation methods, calcination and hydrotreatment. Samples were conditioned by a final calcination step in order to get free of surface anion impurities and their structural properties characterized by a combined X-ray diffraction (XRD), scanning (SEM) and transmission (TEM) microscopy, X-ray energy dispersive (XEDS), X-ray photoelectron (XPS), and diffuse reflectance infrared Fourier transform (DRIFFS) Study. The structural characterization was used to interpret the UV-vis spectra. The resulting joint information allowed the rationalization of the photocatalytic activity observed for the visible-light-assisted liquid-phase degradation of phenol. We founded that maximization of photoactivity is not related with the net absorption power of our systems in the visible range but mostly driven by a combination of two characteristics; the adequate morphological properties and the presence of negatively charged N-containing species.