Highly ordered arrays of 3D faceted nanoparticle supercrystals are formed by self-assembly with controlled nanoparticle packing and unique facet dependent optical property by using a binary solvent diffusion method. The binary diffusion results in supercrystals whose size and quality are determined by initial nanoparticle concentration and diffusion speed. The supercrystal solids display unique facet-dependent surface plasmonic and surface-enhanced Raman characteristics. The supercrystals have potential applications in areas such as optics, electronics, and sensor platforms.