In this work, supramolecular L-L-diphenylalanine (Phe-Phe) nanostructures were self-assembled in solvents of distinct polarity and in the presence of luminescent additives of distinct conjugation length that physically adhere to the nanostructures to provide growth environments of distinct properties. When the additive is poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], an electron donor polymer, and solvent is tetrahydrofuran (THF), Phe-Phe vesicle-like structures are obtained, whereas in water and in the presence of a similar additive in structure, poly[5-methoxy-2-(3-sulfopropoxy)-1,4-phenylenevinylene], nano-tubes are formed. In contrast, when 9-vinyl-carbazole, an electron acceptor additive is used, nano-tubes are formed even when THF is the solvent. The same structures are obtained when the additive is the macromolecule poly(vinyl carbazole). The morphologies of these self-assembled structures were observed by scanning electron microscopy, and their photophysical behavior was determined by steady-state fluorescence spectroscopy and time-resolved fluorescence spectroscopy. These data analyzed altogether inform about the formation mechanisms of such structures and about the influence that distinct interactions exert on self-assembling and charge-transfer processes through formation of complexes between the luminescent additives and the Phe-Phe nano- and microstructures Ver menos