The aim of this work was to synthesize of nanostructured MoO3/TiO2–SiO2 composites with hollow spherical shape by thermal decomposition of anion exchangers saturated with Mo7O6 24 ions and treated with the TBT–TEOS sol. The effect of the kinetics (Kissinger and the Metzger-Horowitz methods) of thermal decomposition of resins of porous and gel structures on the size of MoO3 nanoparticles and the strength of MoO3/TiO2–SiO2 spheres was shown. The formation of dense spherical nanostructured agglomerates of the composite is facilitated by reactions occurring at the interface between the phases of cylindrical and spherical symmetry when using an anion exchange resin with a porous structure. The decomposition reactions of the anion-exchange resin of the gel structure, accompanied by random nucleation, lead to the formation of hollow spherical agglomerates of the composite with cracks on the surface. The materials were characterized by DSC–TGA, XRD and SEM.