Herein, a novel Ti/black TiO 2 -PbO 2 micro/nanostructured photoanode with tunable hydrophobic/hydrophilic characteristics was fabricated via the facile hydrothermal strategy. The tunable hydrophobic/hydrophilic feature of black TiO 2 /PbO 2 architecture is realized by changing loadings of flower-like PbO 2 microspheres. Interestingly, the density functional theory (DFT) calculations demonstrated that H 2 O molecules prefer to adsorb on the surface of black TiO 2 nanosheets, and easier to form hydroxyl radicals on the surface of PbO 2 . Thus, a cooperation action between black TiO 2 and PbO 2 regarding the generation of hydroxyl radical (·OH) by water photoelectrolysis occurs as follows: the black TiO 2 nanosheet layer can be acted as the supply station of water and rapidly transfer the water molecules to neighboring PbO 2 (acted as generation center of hydroxyl radical) to generate hydroxyl radical. Obviously, the division of labor and cooperation between black TiO 2 and PbO 2 is helpful to improve the generation efficiency of hydroxyl radical. Furthermore, the constructed black TiO 2 -PbO 2 architectures have large electroactive areas, low charge transfer resistance, and high separation efficiency of induced carriers. The black TiO 2 -PbO 2 micro/nanostructure obtained under optimum conditions (Ti/black TiO 2 -PbO 2 -180 min) has the highest PEC removal rate of dye (86.24%); an enhancement of approximate 30% is achieved as compared with that of pure black TiO 2 (65.20%). These new findings not only make Ti/black TiO 2 -PbO 2 a more attractive photoanode but, most significantly, also provide promising strategy for designing photoanode. Graphical abstract A novel Ti/black TiO 2 -PbO 2 micro/nanostructured photoanode with tunable hydrophobic/hydrophilic characteristics was fabricated via the facile hydrothermal strategy. The tunable hydrophobic/hydrophilic feature of black TiO 2 /PbO 2 architecture is realized by changing loadings of flower-like PbO 2 microspheres. Interestingly, the density functional theory (DFT) calculations demonstrated that H 2 O molecules prefer to adsorb on the surface of black TiO 2 nanosheets, and easier to form hydroxyl radicals on the surface of PbO 2 . Thus, a cooperation action between black TiO 2 and PbO 2 regarding the generation of hydroxyl radical (·OH) by water photoelectrolysis occurs as follows: the black TiO 2 nanosheet layer can be acted as the supply station of water and rapidly transfer the water molecules to neighboring PbO 2 (acted as generation center of hydroxyl radical) to generate hydroxyl radical. Obviously, the division of labor and cooperation between black TiO 2 and PbO 2 is helpful to improve the generation efficiency of hydroxyl radical. Furthermore, the constructed black TiO 2 -PbO 2 architectures have large electroactive areas, low charge transfer resistance, and high separation efficiency of induced carriers. Thus, the black TiO 2 -PbO 2 micro/nanostructured photoanode exhibited higher photoelectrochemical (PEC) activity, better reproducibility, and obvious photoelectric synergism for the decolorization of dye (reactive brilliant blue KN-R aqueous solution), as compared with black TiO 2 .