The location of nine chiral penta(ethylene oxide) side chains at the periphery of a C 3 -symmetrical hydrogen-bonded extended core gives rise to a thermotropic discotic liquid crystalline material that shows lyotropic phases in polar, protic media. The molecular stacks self-assemble in a reversible and hierarchical fashion, and specific and subtle solvent-molecule interactions together with the created hydrophobic microenvironment account for an unprecedented stabilization of a preferred handedness of the helical stacks by cooperative intermolecular interactions. The presence of either chirality or achirality at the supramolecular level in the stacks can be tuned by temperature and solvent as judged from circular dichroism spectroscopy. A hierarchical growth of the self-assembly is revealed using a variety of spectroscopic techniques and differential scanning calorimetry.