New nanocomposites containing sandwich-type polyoxometalate of [(PW9O34)2(HOSnIVOH)3]12− ( P2W18Sn3) loaded onto Ln-doped TiO2 (Nd, Sm, Dy, Tb) nanoparticles were synthesized and their catalytic activities were assessed. The Ln–TiO2 nanoparticles and Ln–TiO2/P2W18Sn3 nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, field emission scanning electron microscope, energy dispersive analysis of X-rays spectra and diffuse reflectance spectra. The photocatalytic efficiency of the Ln–TiO2 and Ln–TiO2/P2W18Sn3 were examined in the photodegradation of methyl orange and methylene blue solutions. It was revealed through different characterization techniques that the P2W18Sn3 was successfully loaded on the lanthanide-doped anatase phase TiO2 nanoparticles and the particles diameter were relatively 20–30 nanometers. It was revealed that doping by the lanthanide ions followed by loading of polyoxometalates improves the photocatalytic performance of TiO2 effectively. The effects of operational parameters and the kinetics of photocatalytic degradation under UV light were discussed. The prepared nanocomposites were stable and could be easily separated from the reaction system.