Nanostructured dipeptide self-assemblies exhibiting quantum confinement are of great interest due to their potential applications in the field of materials science as optoelectronic materials for energy harvesting devices. Among those, aromatic cyclo-dipeptides containing the amino acid tryptophan are wide-band gap semiconductors displaying high mechanical rigidity, photoluminescence and piezoelectric properties to be used in power generation. In this work, we report the fabrication of hybrid systems based on chiral cyclo-dipeptide L-Tryptophan- L-Tryptophan incorporated into biopolymer electrospun fibers. The micro/nanofibers contain self-assembled nanospheres embedded into the polymer matrix are wide-band gap semiconductors (gap energy 3.8 eV), display blue photoluminescence and relevant piezoelectric and pyroelectric properties with coefficients as high as 57 pCN-1 and 35×10-6 Cm-2k-1, respectively. They are therefore promise systems for thermal sensing and energy harvesting applications.