It is demonstrated that bimetallic silver-gold anisotropic nanostructures can be easily assembled from various nanoparticle building blocks with welldefined geometries by means of electrostatic interactions. One-dimensional (ID) silver nanowires, two-dimensional (2D) silver nanoplates, and spherical gold nanoparticles are used as representative building blocks for bottom-up assembly. The gold nanoparticles are electrostatically bound onto the ID silver nanowires and the 2D silver nanoplates to give bimetallic nanostructures. The unique feature of the resulting nanostructures is the particle-toparticle interaction that subjects absorbed analytes to an enhanced electromagnetic field with strong polarization dependence. The Raman activity of the bimetallic nanostructures is compared with that of the individual nanoparticle blocks by using rhodamine 6G solution as the model analyte. The Raman intensity of the best-performing silver-gold nanostructure is comparable with the dense array of silver nanowires and silver nanoplates that were prepared by means of the Langmuir-Blodgett technique. An optimized design of a single-nanostructure substrate for surface-enhanced Raman spectroscopy (SERS), based on a wet-assembly technique proposed here, can serve as a compact and low-cost alternative to fabricated nanoparticle arrays. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.