ZnO hollow spheres and porous nanosheets were prepared by sonochemical deposition approach and hydrothermal method, respectively. Their photodegradation efficiencies for rhodamine B dye aqueous solutions under UV light irradiation were investigated in detail. Compared with ZnO porous nanosheets, the ZnO hollow spheres exhibited a relatively higher photocatalytic activity. Both absorption and photoluminescence results testified that the synergistic effects of absorption capacity and intrinsic defects finally determined the photocatalytic activity of ZnO hollow spheres.