Ag nanoparticles (Ag-NPs) decorated ZnO microspheres (ZnO-MSs) heterostructural composites were fabricated via a two-step chemical method. The ZnO-MSs with the diameter about 700 nm was initially prepared by ultrasonic technology. Subsequently, Ag-NPs with a diameter of 20-50 nm were anchored onto the surface of the as-prepared ZnO-MSs by a microwave polyol process. The morphology, structural and optical properties of the as-synthesized materials were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), UV-visible absorption spectroscopy, and photoluminescence spectroscopy. The results show that the surface plasmon absorption band of Ag/ZnO composites is distinctly broadened and the PL intensity of Ag/ZnO heterostructural composites varies with the increase of Ag loading. The photocatalytic activity of the Ag/ZnO composites were evaluated by the degradation of rhodamine B (RhB) solution under ultraviolet (UV) and visible light irradiation. The rate of degradation of the as-prepared Ag/ZnO composites was more than triple times faster than that of pure ZnO-MSs under UV light, which was ascribed to the formation of Schottky barriers in the regions between Ag-NPs and ZnO-MSs. Furthermore, Ag/ZnO composites exhibit superior photocatalytic activity over ZnO-MSs in the visible light region owing to the effective electron transfer from plasmon-excited Ag(0) nanoparticles to ZnO-MSs by strong localization of surface plasmon resonance (SPR). This can effectively decrease the recombination of electron-hole pairs, lead to a prolonged lifetime of the electron-holes pairs that promotes the degradation efficiency. The chemical stability and reusability of Ag/ZnO powders were also investigated. (C) 2015 Elsevier B.V. All rights reserved.