This study presents a simple benchtop synthetic protocol for the fabrication of silver (Ag) hierarchical structures in aqueous media using environmentally friendly and inexpensive reagents under mild experimental conditions. Natural organic acids that are known to be present in plants were employed as reducing and morphology-directing reagents. SEM and TEM imaging revealed that the products are three-dimensional hierarchical structures that were formed from self-assembly of smaller nanoparticles. They are generally spherical in shape, measure around 1.5 to 5 ÎŒm in size, and possess highly roughened surfaces due to the interstitial gaps between their nanoparticle subunits. Their hierarchical architecture allows for strong absorption of light in a broad range of wavelengths that extends to the near-infrared region. In addition, their surface morphology has an abundance of hot spot regions, which are capable of inducing strong SERS enhancement effects. The green-synthesized Ag nanostructures showed remarkable SERS activity when used as substrates for the detection of rhodamine 6G dye, a highly toxic water contaminant, even at a concentration as low as 10â8 M. Overall, this study does not only provide a greener approach to Ag hierarchical structures, but also demonstrates the immense potential of these nano-assembled architectures in the sensitive detection of organic dye pollutants.