Heterostructured metallic silver-layered bismuth niobate two-component system (Ag/Bi5Nb3O15) was developed for the first time by a mild hydrothermal method combined with photodeposition. The Ag/Bi5Nb3O15 exhibited single-crystalline orthorhombic structure with small particle size (50-200nm) and octahedral as well as sheet-like shape; additionally, it possessed photoresponse in both UV and visible region. As a novel alternative photocatalysts to TiO2, the photocatalytic activity of the Ag/Bi5Nb3O15 was evaluated by the degradation of tetrabromobisphenol A. a member from the family of the brominated flame retardant, under solar simulating Xe lamp irradiation, and enhanced photocatalytic activity in compared to Bi5Nb3O15 itself and Degussa P25 was obtained. (C) 2011 Elsevier B.V. All rights reserved.