Three-dimensional Bi2O3/TiO2 hierarchical composites have been successfully prepared by a two-step hydrothermal method and subsequent calcination. The samples were characterized using XRD, SEM, TEM, EDS, BET and DRS. The measurement results signified that heterojunctions of various morphologies beta-Bi2O3 growing on the three-dimensional hierarchical anatase Ti2O3 nanorods arrays on FTO glass were apparently formed. The morphology of Bi2O3 changed from three-dimension flower-like microstructures to the sphere-like nanoparticles as the Li(OH) dosage increased. The photocatalytic results showed that all samples exhibited much higher photocatalytic activities than that of pure Bi2O3 and TiO2 (P25) in photocatalytic degradation of methyl blue (MB) under visible-light irradiation. Whereas BTL4 sample exhibited the highest photoactivity with increasing the dosage of Li(OH) to 2 mmol. Furthermore, the absorption edge of the Bi2O3/TiO2 series composites displayed a broad-spectrum photoabsorption from UV to visible-light compared with the individual component. The as-synthesized Bi2O3/TiO2 composites possessed excellent photocatalytic activity and outstanding recyclability. The enhanced photocatalytic efficiency was mainly attributed to the Bi2O3/TiO2 p-n heterojunctions and hierarchical nanostructure. The recombination of photogenerated electron-hole pairs was efficiently suppressed by the Bi2O3/TiO2 p-n heterojunctions. (C) 2017 Elsevier B.V. All rights reserved.