A mesoporous TiO2–SiO2 nanocomposite photocatalyst has been prepared from TiO2 nanoparticles and ethoxysilane oligomers in the presence of a non-ionic surfactant (n-octylamine). The 2D and 3D structure properties of the resulting nanomaterial are described. The use of 3D techniques, particularly HAADF-STEM electron tomography, together with 3D reconstructions and atomic force microscopy, provides insight into the fine structure of these materials. We find that n-octylamine creates a mesoporous silica structure in which titania nanoparticles are embedded, and that some of the titania is retained on the outer surface of the material. Rapid photodegradation of methylene blue dye is facilitated, due to the synergistic effect of: (1) its adsorption into the composite mesoporous structure, and (2) its photodegradation by the superficial TiO2.