The Mo-doped Bi2WO6 three-dimensional (3D) hierarchical microspheres from nanoplates have been synthesized by a hydrothermal route. The products were characterized in detail by multiform techniques: X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDS), scanning electron microscopy (SEM), and UV-vis absorption spectrum. The results of the photocatalytic degradation of Rhodamine-B (RhB) in aqueous solution showed that molybdenum ions doping greatly improved the photocatalytic efficiency of Bi2WO6 3D hierarchical microspheres. The Mo-doped Bi2WO6 microspheres with atomic ratio of Mo-W of 0.05 had the best activity in photodegradation of RhB in aqueous solution under 500 W Xe lamp light irradiation. (C) 2011 Elsevier B.V. All rights reserved.