Highly efficient Bi₂WO₆-TiO₂ heterostructure is synthesized by means of a hydrothermal method having highly photoactivity for the degradation of Rhodamine B under sunlike irradiation. From the structural characterization it has been demonstrated that TiO₂ is incorporated on the Aurivillius structure. Interesting synergetic effect between TiO₂ and Bi₂WO₆ leads to an improved charge carrier separation mechanism, causing the excellent photocatalytic performance under sunlike irradiation. The photocatalytic performance of Bi₂WO₆ and Bi₂WO₆-TiO₂ was compared under different irradiation conditions and using increasing Rhodamine B concentration up to 25ppm. After the photocatalytic analysis of both systems, the mineralization efficiency of the heterostructure appears significantly higher with respect to Bi₂WO₆.