We developed a cheap and rapid method for the fabrication of 3D nanoparticle superlattices (SLs) of Au@SGAN and Au@MSA (N-acetyl glutathione (SGAN) and mercaptosuccinic acid (MSA) protected gold nanoparticles, respectively) in gram scale, at a liquid-liquid interfaces under flowing nitrogen gas. While available methods take several weeks to make crystalline SLs, the present route makes them in a day. Morphology of these crystals was examined with scanning electron microscopy (SEM), and their structures were probed using transmission electron microscopy (TEM). The surface enhanced Raman scattering (SERS) studies of these crystals were done using crystal violet (CV) molecules as the analyte which exhibited a detection limit of 10-8 M. The SERS spectrum was used to map the Raman images of the superlattce crystals. SERS from the edges of the crystal showed more enhancement than from the flat surfaces, which is in good agreement with theoretical reports of such anisotropic structures. The sides of the crystals are not sharp, and they show corrugations at the nanometer scale. This helps to produce more "hot spots" at the edges, which result in larger electric field enhancement from these locations. The enhancement factors (EF) for Au@MSA and Au@SGAN SLs were calculated to be around 1.47 x 106 and 3.60 x 105, respectively. More enhancements from Au@MSA SL compared to that of Au@SGAN could be attributed to the smaller chain length of the MSA molecule, which allows closer analyte approach to the nanoparticle surface. © 2009 American Chemical Society.