Porous 3D flower-like Ag/ZnO heterostructural composites were fabricated by hydrothermal and photochemical deposition methods, without using any pore-directing reagents and surfactants. The obtained samples were characterized by XRD, SEM, TEM, XPS, BJH, DRS, and PL spectrum. The experiment results show that the silver nanoparticles successfully load on the surface of assembled ZnO flowers. The TEM and SEM morphologies demonstrated unique porous 3D flower-like structure of Ag/ZnO. Such special structure makes larger surface area and more active sites exposed during the reaction, facilitating the transportation of reactants and products and increasing the reaction rate. The photocatalytic degradation experiments under UV irradiation using Rhodamine B (RhB) as a model dye were executed. The relative results demonstrate that the photocatalytic activity of Ag/ZnO is obviously improved compared with the pure ZnO and the commercial TiO2(Degussa P25), the AZ-15 sample has the highest photocatalytic activity. The Ag/ZnO heterostructure composites promoted the separation of photo-induced electrons and holes, which was proved by photoluminescence spectra (PL). (C) 2015 Elsevier B.V. All rights reserved.