Hierarchical Ag/Bi2WO6 nanomaterials were prepared by a facile one-step hydrothermal method in mixed acetic acid and ethylene glycol (EG) medium. EG is employed as mild reducing agent for the formation of metallic Ag from Ag+ precursors. In situ energy dispersive X-ray diffraction (EDXRD) monitoring showed that the hydrothermal formation kinetics of Bi2WO6 in the presence of EG was significantly slowed down due to its very high viscosity. The photocatalytic activities of Ag/Bi2WO6 composites were evaluated by the photodegradation of methylene blue (MB) under visible light irradiation. The photocatalytic activity of Bi2WO6 is strongly influenced by the Ag loading. The enhanced catalytic activity of the composites is based on the cooperative effects of plasmon absorption band and separation of photogenerated electron-hole pairs.