Self-assembly of nanorods (NRs) enhanced by functionalization with liquid crystals (LC) ligands has been demonstrated. First, CTAB (cetyltrimethylammonium bromide) coated gold NRs were prepared in water through a modified one-step seed growth process. The hydrophilic GNRs were then converted into hydrophobic NRs employing a surface modification process using liquid crystalline organosilanes. The functionalized GNRs were characterized by TEM (transmission electron microscopy) and SAXS (small angle X-ray scattering) to investigate the packing mode of the GNRs. The results propose models of the assembly of the GNRs depending on nature and connectivity of the attached liquid crystal molecules. Furthermore, a macroscopic orientation of the GNRs doped in LC was achieved via an alignment technique of the liquid crystal host. SAXS analysis of the doped DLC indicated modification of lattice parameters due to the insertion of the DLC-GNRs, which resulted in an enhancement of the charge carrier mobility.