In this work, TiO₂ and Anderson-type polyoxometalates (Ni, Co, and Fe) thin-film composites were fabricated. The composites were characterized by FTIR and Raman spectroscopy, diffuse reflectance, and scanning electronic microscopy. The methylene blue (MB) photocatalytic degradation on the composites under UV irradiation was studied. Spectroscopic results verified the modification of TiO₂ thin films. Optical and morphological properties changed after TiO₂ modification. The largest change in the optical band gap was observed for the FePOM/TiO₂ system, which reported a value of 3.05 eV. The POM/TiO₂ systems were more efficient in methylene blue (MB) adsorption than bare TiO₂. Furthermore, the modified films were more efficient than bare TiO₂ during MB photodegradation tests. The NiPOM/TiO₂ and the CoPOM/TiO₂ were the most efficient in the MB adsorption, reaching ~20%. The NiPOM/TiO₂ and the CoPOM/TiO₂ composites were the most efficient in the photodegradation process, reaching ~50% of MB removal. The stability tests indicated that composite films were moderately stable after the three performed reusability cycles. Thus, these results suggest that POM modification of TiO₂ can improve the adsorption and photodegradation capacity of semiconductors.