In the development of functional materials, side chains are traditionally incorporated into the primary chemical structure to induce liquid-crystalline behavior or to enhance solubility for improved processability. However, emerging evidence suggests that side chains play a far more complex role. This study presents a case of a double helical supramolecular structure formed by star-shaped mesogens in the absence of specific interactions. The molecular conformation is primarily dictated by the self-assembly of the side chains, introducing a new organizational paradigm for semiflexible low-molecular-weight mesogens.