1wileyonlinelibrary.com signifi cant interest over the past few years for the creation of metamaterials, [ 2 ] for optical applications, such as high effi ciency polarizers [ 3 ] and display applications, [ 4 ] as well as for applications in surface-enhanced Raman spectroscopy. [ 5 ] However, the assembly and manipulation of anisotropic building blocks into complex superstructures is still a challenging task in comparison to their corresponding quasi-spherical counterpart nanoparticles. [ 6 ] The key-limiting factor most often described is the irreversible aggregation of the anisometric nanomaterial in a given fl uid or polymer host medium. It is well understood that the interactions between nanostructures plays a critical role during the self-assembly process. [ 7 ] Ionic additives [ 8 ] or cationic surfactants [ 9 ] have been employed to tune the attraction between nanoparticles in colloidal suspensions and improve the ability of inducing nanorods assemblies.In an earlier paper, we reported a fascinating large-area selfassembly of nematic liquid crystal (LC)-functionalized gold nanorods (GNRs) forming nematic-and smectic-like patterns on substrates, and nematic-phase behavior in the bulk. [ 10 ] The interaction between the LC molecules attached to the surface of the GNRs was established as the driving force for the selfassembly of such GNRs. The attached LC ligands tended to pack together next to each other when the GNRs dispersion became more and more concentrated during solvent evaporation, and attractive interactions between the capping LC ligands facilitated the formation of large-area nematic and smectic superstructures of the GNRs. To extent this concept to higher ordered LC phases that would facilitate long-range order, alignment, and even enhanced photoconductivity, we here present the synthesis, characterization, as well as the surface and bulk self-assembly of GNRs functionalized with discotic triphenylene-based LC (DLC) molecules ( Figure 1 a). Strong π-π interactions between the triphenylene cores should aid the selfassembly as well as integration and alignment in structurally identical triphenylene hosts. Yamada et al. [ 11 ] reported a 2D hexagonal superstructure of such DLC-functionalized gold nanoparticles on the substrate of transmission electron microscopy Gold nanorods functionalized with triphenylene-based discotic liquid crystal (LC) motifs show striking self-assembly behavior both on transmission electron microscopy (TEM) grids as well as in the bulk enforced by the π-π-stacking of triphenylene groups of adjacent nanorods. TEM images confi rm that these discotic LC nanorods form ribbons of parallel-stacked nanorods several hundred nanometer long. The pursued silane conjugation approach to decorate the nanorods allows for the preparation of dispersions of the nanorods in the hexagonal columnar phases of parent discotic LCs, where the nanorods can be macroscopically aligned with almost 80% effi ciency by a simple shearing protocol. Doping the parent host materials with about 1% by weight...