Anatase TiO2-modified flower-like Bi2WO6 nanostructures were prepared by a simple hydrothermal reaction followed by layer-by-layer deposition and calcination. The photocatalytic activity was evaluated using Brilliant Red X3B, an anionic azo dye, as the target organic pollutant under UV-Vis light irradiation. The experiment results showed that the photocatalytic activity of the hybrid increases first and then decreases with increasing loading amount of TiO2. The hybrid coated with four layers of TiO2 (containing 20wt-% TiO2) showed the highest photocatalytic activity, which is 10.45 and 3.20 times higher than that of pure Bi2WO6 and TiO2, respectively. The improved photocatalytic performance of TiO2-modified Bi2WO6 nanostructures could be ascribed to the improved light-harvesting ability, efficient photo-generated electron-hole separation, and enhanced adsorption of the dye. This work may shed light on the design of complex architectures and the exploitation of their potential applications.