The design and synthesis of giant well-defined molecular architectures requires a balanced choice between covalent synthesis and the self-assembly of the fragments prepared. A number of supramolecular architectures will be discussed in which peripheral chirality is expressed at the supramolecular level and in which it is possible to amplify this chirality in an unprecedented way. We have come to general design rules for the synthesis of chiral self-assembled polymers by the cooperative stacking of hydrogen-bonded pairs; design rules that are operative in both apolar and polar solvents. In polar solvents, like water, it is evident that the supramolecular architectures are formed in a hierarchical fashion. Spectroscopic evidence will be presented to confirm the hierarchical growth. In an attempt to arrive at functional architectures, we have included p-conjugated fragments in the molecules, leading to materials that possess instructed mesoscopic morphology.