A major challenge in nanoparticle self-assembly is programming the large-area organization of a single type of anisotropic nanoparticle into distinct superlattices with tunable packing efficiencies.Thenanoscale surface chemistry have been demonstrated todirect the self-assembly of silver octahedral into three distinct two –dimensional plasmonic superlattices at liquid/liquid interface.Systematically changing surface capping agents of silver octahedral leads to a continuous superlattice structural evolution,from close-packed to progressively open structures.