This study is devoted to the preparation of strong spherical composites V2O5/TiO2–SiO2 by a combined template and sol-gel method. The composition, size and shape of the colloidal particles in butanol ash with tetrabutoxytitanium and tetraethoxysilane, as well as the physicochemical processes leading to the strengthening of the spherical agglomerates obtained using an anion exchanger with a gel structure, have been determined. Electrophoresis, small-angle X-ray scattering, and viscometry were used to demonstrate the presence in the sol of positively charged colloidal particles of lenticular and cylindrical shape, whose size, when the sol is stabilised, reaches 53 Å. The absorption of the sol by the anion exchanger in vanadium form is due to the equalisation of the osmotic pressure in the anion exchanger/sol system. Spherical composites with a diameter of 300 µm were obtained. It was shown by X-ray diffraction that the composites consist of V2O5 with an orthorhombic structure, TiO2 with an anatase structure, and amorphous silicon dioxide. The interaction at the interface between the phases of V2O5 with TiO2 and SiO2, which leads to the strengthening of the sphere of the V2O5/TiO2–SiO2 composite, has been demonstrated by IR and Raman spectroscopy. The results obtained can be used for the synthesis of MxOy/TiO2–SiO2 oxide composites with spherical agglomerates.