Mesoporous nanosized TiO2 and ZnxTi1-xO2-x solid solution having a Zn content below 10 mol % with a particles size between 13 and 17 nm are prepared by a template-free sol-gel method followed by high-temperature supercritical drying in 2-propanol. The structural, textural, and electronic properties of the obtained nanomaterials are methodically investigated by using XRD, SEM, TEM, ED, HREM, EDX, ICP-OES, N-2 adsorption-desorption, Raman spectroscopy, and diffuse reflectance UV-vis spectroscopy. It is shown that the proposed synthesis technique leads to the formation of a ZnxTi1-xO2-x solid solution based oil the anatase crystal structure rather than a two-phase sample. High-resolution electron microscopy and electron diffraction indicate that the distribution of zinc atoms over the anatase structure does not lead to a considerable deformation of the crystal structure.