Nest-like Bi2WO6 microspheres were successfully synthesized through a simple one step template-free approach employing a hydrothermal process, and it is found that citrate and NaHCO3 played multifold roles in the formation process of the nest-like microspheres. A formation mechanism of nested Bi2WO6 hierarchical microspheres was proposed based on XRD analysis and SEM observation of the products of different reaction conditions. The UV-vis diffuse reflectance spectra indicated that the as-synthesized microspheres have a significantly enhanced optical absorbance in the UV-vis region and red-shift phenomenon compared to that of Bi2WO6 powder prepared by the surfactant reaction method. The nest-like Bi2WO6 microspheres exhibited good photocatalytic activity in the degradation of Rhodamine-B (RhB) under 500 W Xe lamp light irradiation.