We report herewith tryptophan (Trp)-conjugated peptidomimetics that show intramolecular through-space association between the Trp units. Our investigation revealed that the proximal placement of Trp can lead to the emergence of a new and unanticipated fluorescent entity constituting a Trp-Trp dimer. Proton-induced modulation of fluorescence is a consequence of this work. Investigations with control compounds unequivocally revealed that the fluorescence property is not originated from the localized excited state but from the unprecedented Trp-Trp intramolecular dimer in the ground state itself. The present findings will initiate the biophysical scientists to have a relook at the fluorescence properties of Trp-containing proteins.