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V-TiO₂ photocatalyst with 0 ≤ V ≤ 20 mol% was prepared via the sol–gel method based on mixed oxide titanium–vanadium nanoparticles with size and composition control. The mixed oxide vanadium–titanium oxo-alkoxy nanonoparticles were generated in a chemical micromixing reactor, coated on glass beads via liquid colloid deposition method and underwent to an appropriate thermal treatment forming crystallized nanocoatings. X-ray diffraction, Raman, thermogravimetric and differential thermal analyses confirmed anatase crystalline structure at vanadium content ≤ 10 mol%, with the cell parameters identical to those of pure TiO₂. At a higher vanadium content of ~20 mol%, the material segregation began and orthorhombic phase of V₂O₅ appeared. The crystallization onset temperature of V-TiO₂ smoothly changed with an increase in vanadium content. The best photocatalytic performance towards methylene blue decomposition in aqueous solutions under UVA and visible light illuminations was observed in V-TiO₂ nanocoatings with, respectively, 2 mol% and 10 mol% vanadium.