Condensed aggregates of periodically organized nanostructures are among the most important research topics for the development of nanoengineering and dynamic control of physicochemical properties. The range of application could be broader if they form well defined, large-scale structures. We show that spherical nanoparticles can organize into many diverse structures when substituted by mesogenic ligands, due to the self-segregation of chemically non-compatible units. Nematic, smectic columnar and 3D superstructures were observed in which metal cores and organic parts self-segregate in space. The type of structure can be controlled by composition of grafting layer and temperature as well as by the metal core size and density of grafting layer. In special cases the distance between nanoparticles in the superlatice could be controlled by light-driven conformational changes in organic grafting layer (azobenzene derivatives), that gave possibility to control the plasmonic properties of hybrid materials. We show strategies used to synthesize liquid-crystalline nanoparticles as well as discuss parameters influencing structural and thermal characteristic of aggregates. We also demonstrated that the liquid-crystalline approach offers access to dynamic self-assembly and metamaterials with anisotropic plasmonic properties, which makes this strategy unique among others.