ZnO nanostructures materials with two-dimensional (2D) plate-like and three-dimensional (3D) flower-like morphologies have been synthesized via facile hydrothermal process. Scanning electron microscopy (SEM), high resolution transmission electron microscope (HRTEM) and X-ray diffraction (XRD) have been used to characterize the samples. We have compared the surface photoelectric properties of flower-like ZnO with that of plate-like ZnO by means of surface photovoltage (SPV), field-induced surface photovoltage (FISPV), transient photovoltage (TPV) and surface photocurrent (SPC) techniques. Based on the photovoltage responses, the influence of the morphology on transfer characteristics of photogenerated charge carriers was discussed. The synthesized flower-like ZnO exhibited more efficient separation and transfer properties of photogenerated charge carriers than that of plate-like ZnO in the UV region due to the special flower-like hierarchical nanostructures. We have also evaluated the photocatalytic activity of the ZnO samples by photodegradation efficiency of RhB. The experiments demonstrated that RhB in aqueous solution was more efficiently photodegraded using flower-like ZnO than plate-like ZnO. The results also show the consistency between the carrier dynamics of photogenerated electron-hole pairs and photocatalytic activity. (C) 2011 Elsevier B.V. All rights reserved.