The realization of long, aligned molecular wires is a great challenge, and a variety of approaches have been proposed. Interestingly, hexapentyloxytriphenylene (HAT5) discotic liquid crystal molecules, a model system of molecules with flat and aromatic cores, can spontaneously form well-aligned, micrometer long, yet only tens of nanometers thick, nanowires on solid surfaces. We have investigated the formation mechanism of these wires using different solvents with selected characteristics, including chemical structure, boiling point, vapor pressure, and surface tension. When casting frorn toluene and benzene solutions, atomic force microscopy reveals that the discotics spontaneously form very long and thin wires, self-aligning along a common orientation. If instead dodecane or heptane are used, different and in general thicker structures are obtained. The chemical structure of the solvent appears to have a key role, coupling to the liquid crystal self-assembly by allowing solvent molecules to enter the ordered structure if their design matches the core of HATS molecules, thereby guiding the assembly. However, other aspects are also relevant in the assembly, including the nature of the substrate and the rate of solvent evaporation, and these can favor or interfere with the self-assembly into long structures. The use of solvents with aromatic structure is advantageous not only because it affects the geometry of the assembly, promoting long wire formation, but it is also compatible with good quality of the intermolecular order, as suggested by a high anisotropy of the Raman spectra of the nanowires formed from these solvents. Finally, the electrical properties of ordered systems show a clearly higher electrical conductivity compared to the disorganized aggregates.