Highly efficient Bi(2)WO(6)-TiO(2) heterostructures are synthesized by means of a hydrothermal method; they have high photoactivity for the degradation of rhodamine B under sunlike irradiation. An interesting synergetic effect between TiO(2) and Bi(2)WO(6) leads to an improved charge carrier separation mechanism, causing the excellent photocatalytic performance.