Abstract <p>Materials based on hydrated silica containing organic groups of varying nature and size were obtained, including hydrophobic hydrocarbon groups (vinyl- and dodecyl-) and fluorine-containing groups (3,3,3-fluoropropyl- and 1H, 1H, 2H, 2H-perfluorodecyl-), as well as hydrocarbon groups containing proton-acceptor groups (3-aminopropyl- and 3-(phenylamino)propyl-). The thermal stability of the resulting materials was demonstrated up to temperatures of 300°C. The introduction of small hydrophobic fragments onto the silica surface provides highly dispersed materials with specific surface areas reaching up to 675 m²/g. Increasing the size of the hydrocarbon or perfluorinated groups leads to the formation of superhydrophobic materials exhibiting water contact angles as high as 174°. It was shown that the incorporation of silica modified with 1H, 1H, 2H, 2H-perfluorodecyl groups into a styrene–ethylene–butylene–styrene block copolymer matrix enhances the hydrophobicity of the resulting films from 105° to 137°.</p>