The thin-film directed self-assembly of molecular building blocks into oriented nanostructure arrays enables next-generation lithography at the sub-5 nm scale. Currently, the fabrication of inorganic arrays from molecular building blocks is restricted by the limited long-range order and orientation of the materials, as well as suitable methodologies for creating lithographic templates at sub-5 nm dimensions. In recent years, higher-order liquid crystals have emerged as functional thin films for organic electronics, nanoporous membranes, and templated synthesis, which provide opportunities for their use as lithographic templates. By choosing examples from these fields, recent progress toward the design of molecular building blocks is highlighted, with an emphasis on liquid crystals, to access sub-5 nm features, their directed self-assembly into oriented thin films, and, importantly, the fabrication of inorganic arrays. Finally, future challenges regarding sub-5 nm patterning with liquid crystals are discussed.