The synergistic effect of polyoxometalate (POM) and metal-doped TiO2 (metal = Zr, Y and Ce) was examined, to fabricate nanocomposites with enhanced photocatalytic activities toward the degradation of methyl orange (MO), as a model textile dye. A series of new nanocomposites, containing different loading amounts of H9Na3[WZn3(H2O)2(ZnW9O34)2].24H2O (HZnW) (10–30%) on each of the metal-doped TiO2 nanoparticles, were synthesized using impregnation method. The morphology and crystal phase of the as-prepared nanocomposites were investigated by various characterization techniques: Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, energy-dispersive X-ray analysis and diffuse reflectance spectroscopy, indicating that the HZnW and metal-doped TiO2 had been successfully incorporated into the nanocomposite structure. The effects of parameters such as loading amount of HZnW, catalyst dose, pH and initial concentration of dye solution were investigated on the degradation kinetics and it was interestingly found that the prepared nanocomposites could efficiently degrade the MO dye in 5–7 min under UV light irradiation. The best results were obtained for the HZnW-Zr-TiO2 among the different nanocomposites. Also, control studies showed the superior photocatalytic properties of composites compared to that of the individual components. The facile preparation and their improved photocatalytic activities suggest that these materials can have a promising future for water and wastewater purifications.