We perform molecular simulations to study the self-assembly of nanoparticles functionalized with oligomeric tethers attached to specific locations on the nanoparticle surface. We demonstrate that for certain categories of tethered nano building blocks the obtained morphologies may be predicted using concepts from block copolymer microphase separation and liquid-crystal phase ordering, whereas for other categories the unique packing constraints introduced by nanoparticle geometry and by nanoparticle−tether topology lead to structures far richer than those found in conventional block copolymer, surfactant, and liquid-crystal systems. Our results suggest the potential usefulness of considering tethered nano building blocks as a new class of “macromolecule” for assembling novel materials on the nanoscale.