This chapter focuses on decorating nanoparticles with synthetic as well as biomacromolecules for controlling interparticle distances and relative orientations in assemblies. It introduces synthetic approaches toward core/shell architectures and shows how macromolecular ligands allow controlling order in 2D and 3D assemblies. The chapter illustrates how symmetries can be broken in order to advance from simple hexagonally close-packed assemblies to systems of higher complexity overvire of the different strategies for coupling macromolecules to nanoparticles in a well-defined fashion, covering both crosslinked and non-crosslinked polymeric coatings. There is special emphasis on core/gel-shell nanoparticles as a versatile class allowing for large interparticle separations and on protein-modified nanoparticles that are particularly well suited for achieving complex symmetries in particle assemblies. Finally, the chapter points out several examples for functionality, not with the aim of completely covering a specific field of applications but rather for the sake of illustrating the underlying concepts for functional material design.