Gold nanoparticles (Au-NPs) prepared by sputter deposition of Au in an ionic liquid were selectively assembled at the edges and vertices of Ag nanocubes, the surfaces of which were modified with a self-assembled monolayer of 1-octadecanethiol and 4-amino-2-mercaptopyrimidine. Chemical etching of Ag from the resulting Au Ag binary nanocomposites resulted in the formation of Au nanoframes.