In this work, the triplet state behavior of naphthalene-based pseudopeptides with amide-based macrocyclic or lateral chain substructures has been investigated in the presence of benzophenone and/or biphenyl, as suitable energy-donating chromophores. Their behavior has been compared with that of 1,4-dimethylnaphthalene as model compound. In all the cases, the triplet–triplet absorption of naphthalene is detected by transient absorption spectroscopy, upon selective excitation of benzophenone at 355 nm. The kinetics of formation and decay of this species is markedly slower in the pseudopeptides, due to retardation of triplet–triplet energy transfer and exciplex formation. Finally, the delayed fluorescence detected in the model naphthalene is absent in the pseudopeptides. The concept can, in principle, be exploited for the study of excited-state interactions in supramolecular systems.