The self-assembly of diaminododecane with dendritic l-lysine-based peptides to form gel-phase materials was investigated in a range of different solvents. The degree of structuring was modulated by the solvent employed, an effect which induced subtle changes in the mesoscale aggregate morphology and macroscopic behavior of the self-assembled state. In this paper a range of different solvent parameters are investigated, and it is clearly shown that macroscopic gelation can be related to a solvent polar solubility parameter for this system. The results also show a dependence on Kamlet-Taft hydrogen bonding parameters, and this clearly demonstrates the role of the solvent environment in terms of dendron--dendron intermolecular hydrogen bonding and its impact on the supramolecular chiral organization of the assembled superstructure.