This paper presents a review of the work published by the authors on the synthesis, characterization and evaluation of the photocatalytic activity of TiO2/SiO2 materials. The use of titania-silica mixed oxides photocatalysts is proposed basically as a process improvement to overcome the difficulties of recovering titania from the slurries after the photocatalytic treatment of contaminated waters. To understand the mechanism governing the photocatalytic activity of these materials, several titania-silica photocatalysts have been prepared through a sol-gel method that allows controlling the main variables to obtain materials with different textural properties, degree of titania incorporation, dispersion of the photoactive phase and crystallinity of titanium dioxide. The samples have been characterized in depth, looking for correlations between the main physicochemical properties (TiO2 crystallite size, band gap energy and titania surface area) and the activity shown in the photocatalytic oxidation of cyanide, selected as model pollutant. The results suggest that the photocatalytic activity is strongly influenced by the quality of the titania crystal network, which in turn is improved by the use of a hydrothermal crystallization procedure. Additionally, the evaluation of the fraction of the total surface area corresponding to titania is mandatory for comparing the catalytic activity of different materials in processes in which titanium dioxide is the only phase catalytically active and silica behaves as an inert support.