Au/Pd octopods were synthesized with enhanced sample homogeneity through the use of aromatic additives. This increase in sample monodispersity facilitates large-area periodic assembly of stellated metal nanostructures for the first time. The aromatic additives were also found to influence the structures of the stellated nanocrystals with subtle shape modifications observed that can alter the packing arrangement of the Au/Pd octopods. These results indicate the possibility of tailored assembly of stellated nanostructures, which would be useful for optical applications that require strong and predictable coupling between plasmonic building blocks.