In this paper, W x Ti 1−x O 2 solid solutions (x=0.000, 0.005, 0.010, 0.015, and 0.020) microspheres were synthesized with an aerosol-assisted flow synthesis method. The resulting samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption, UV–vis diffuse reflectance spectrum (DRS) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities of the as-prepared catalysts were measured by the degradation of rhodamine B (RhB) under visible light irradiation (λ≥420nm). All the solid solutions exhibited higher photocatalytic activities than pure TiO 2 and the W 0.015 Ti 0.985 O 2 solid solution possessed the highest photocatalytic activity. The degradation constant of RhB on W 0.015 Ti 0.985 O 2 solid solution catalyst was about 15 times of that of the pure TiO 2 and 25 times of that of Degussa P25, respectively. This study provides an effective method to prepare visible light photocatalysts on a large scale.