The V−Ti−O system as a product of thermal decomposition of vanadyl and titanyl oxalates at 873 and 1173 K in argon atmosphere was studied by X-ray diffraction and infrared spectroscopy. The results obtained, the analysis and surface measurement data suggest that a V3+−V4+−Ti4+−O solid solution is formed. Spectroscopic measurements reveal the presence of a V=O bond in the system obtained at 873 K.