The aim of the research was to develop the area of mesoporous thin films of a binary TiO2–SiO2 system. Sol was synthesized from tetraethylorthosilicate as the silica source and titanium isopropoxide solution as the TiO2 source, while triblock copolymer surfactant (Pluronic F 127 (10% solution in water, (P))) was used as the mesostructure-directing agent. In this paper we present sol-gel obtained TiO2–SiO2 with a mesoporous structure. The effects of added titanium on the mesostructure and on the porosity are presented and discussed. Four different molar percentage ratios of Ti: Si were used for the synthesis of mixed TiO2–SiO2 mesoporous thin films on glass substrate. The mesoporous structure of thin films was characterized by X-ray diffraction (XRD) patterns, atomic force microscopy (AFM), scanning electron microscopy (SEM) and the water contact angle. These mesoporous TiO2–SiO2 thin films could have many potential applications in many areas such as separation membranes, catalysis, optics, and self-cleaning surfaces.