Bi2WO6 hollow microspheres were successfully synthesized by solvothermal process in the presence of urea at proper ethylene glycol (EG)/absolute ethanol (AE) volume ratio (1:1). The samples consisted of microspheres with an average diameter of 1 mu m, and the shell consisted of numerous nanoplates. The effect of solvent, the ratio of EG/AE solvents and urea amount on the morphology of the samples was studied systematically, indicating that a certain ratio of EG/AE and urea amount played an important role in the formation of hollow microspheres. Based on the detailed investigation, the formation mechanism of the hollow interior by EG-induced Ostwald ripening process was proposed. By contrast, the Bi2WO6 hollow microspheres exhibited higher catalytic activity for degradation of Rhodamine B under xenon lamp irradiation, and nearly 100 % Rhodamine B is degraded within 120 min.