The use of chiral surfactants results in a powerful tool to form chiral assemblies of (L)proline-functionalized porphyrin derivatives in EtOH/H[Formula: see text]O exploiting hydrophobic effect. The formation of chiral heteroaggregated species strictly depends both on the configuration of the chiral center of the surfactant and on its concentration, opening the possibility to tune the supramolecular asymmetry of the final structures.