Self-aggregation has recently emerged as an efficient tool for the production of well-ordered supramolecular structures at the nanometric scale. In this framework, peptides offer important advantages as building blocks because of their biocompatibility and 3D-structural/functional diversities. The chemical diversity of peptides may be further expanded by use of noncoded amino acids. In the present work, we focused our attention on two known photoswitchable azobenzene-containing alpha-amino acids and used them as initiators for the reversible modulation of the cis/trans conformational states of two poly(gamma-benzyl-L-glutamate)-based hybrid molecules with either C2 or C3 symmetry. The microscopic photoresponsive self-assembly of these compounds was examined in detail. Moreover, these hybrids were exploited in the construction of macroscopic supramolecular architectures via the electrospinning technique. Finally, after appropriate thiol functionalization, we fabricated and characterized dimeric and trimeric gold nanoparticle/polypeptide hybrid systems.