The uniform spherical silver three-dimensional (3D) hierarchical structures consisting of dendrites were synthesized for the first time with a very facile, mild and cost-effective wet-chemical method employing potassium biphthalate as the structure-director in aqueous solution and at ambient conditions. The products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), infrared spectroscopy (IR) and energy dispersive X-ray spectroscopy (EDS). The investigation on the morphologies evolution revealed that potassium biphthalate was critical to control the assembly of the hierarchical Ag architectures. The hierarchical structure was shown excellent surface-enhanced Raman scattering (SERS) effect due to intensive hot spots. (C) 2013 Elsevier B.V. All rights reserved.