Chrysanthemum-analogous Bi2O3−Bi2WO6 composite microspheres, assembled by nanosheets, were synthesized through a one-step hydrothermal route with the aid of surfactant templates. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were employed to clarify the structure and morphology of the Bi2O3−Bi2WO6 microspheres. Nitrogen adsorption and desorption isotherms were conducted to examine the specific surface area and the pore nature of the as-prepared microspheres. The photocatalytic activity of the Bi2O3−Bi2WO6 composite microspheres was evaluated by using rhodamine B as a model contaminant, and over 99% of rhodamine B was degraded within 10 min under the exposure of sunlight. The Bi2O3−Bi2WO6 composite microspheres presented enhanced photocatalytic performances compared with separate Bi2O3, Bi2WO6, and conventional P25.