ZnO/Bi2O3 heterojunction was prepared by solid state reaction method at room temperature. The asprepared nanostructures were characterized as the assembled nanosheets of ZnO on which Bi2O3 nanoparticles were well dispersed. Further studies revealed that the morphology and photocatalytic property could be regulated by tuning the amount of Bi2O3. The introduction of Bi2O3 can lead to the enhancement of solar light absorption, and the 5% ZnO/Bi2O3 samples exhibited the best photocatalytic activity under the solar light irradiation. The excellent photocatalytic performances could be ascribed to the synergistic effects of the hierarchical nanostructures and the effective separation of photogenerated carriers. Moreover, the hydroxyl radicals (*OH) are found to be the main active species generated in the oxidation reaction of RhB over ZnO/Bi2O3 photocatalyst. Therefore, our work demonstrated a facile way to prepare hierarchical nanostructures with excellent photocatalytic performance using solid state method at room temperature. (C) 2014 Elsevier Ltd. All rights reserved.