Compositions and technology for obtaining a photocatalytic composite material (PCM) by deposition of titanium dioxide particles synthesized by the sol–gel method on a silica support of various types (microsilica, gaize and diatomite) have been developed. The properties (chemical and mineral composition, dispersion, specific surface area, porosity, ζ-potential, acid–base properties, and microstructure) of microsilica, gaize and diatomite were studied to assess the effectiveness of using a photocatalytic agent as a carrier. In terms of specific viscosity (ηsp = 45), the concentration of the precursor (tetrabutoxytitanium—TBT) is set at 22 vol. % in a solvent (ethanol), at which it is possible to obtain the maximum amount of dissolved film oligomer without the formation of an aggregate-like precipitate. Modification of the reaction mixture (precursor: ethanol = 1:3) by replacing part of the solvent with a Span-60 surfactant/TBT = 1–1.1 made it possible to obtain polydisperse titanium dioxide particles with peak sizes of 43 nm and 690 nm according to laser granulometry data. Taking into account the interaction of titanium complexes with the surface of a silica support, a phenomenological model of the processes of structure formation of a photocatalytic composite material is proposed. By the value of the decomposition of rhodamine B, the photocatalytic activity of the developed composite materials was determined: PCM based on diatomite—86%; PCM based on microsilica—85%; PCM based on gaize—57%.