Hydrobenzophenanthrolinone derivatives were synthesized by three-component condensation of 8-aminoquinoline, aromatic aldehydes, and dimedone. The structures of the obtained substances were confirmed by NMR and IR spectroscopy and mass spectrometry. Spectral-luminescent investigations of the synthesized compounds showed that they were characterized by high oscillator strengths for allowed electronic transitions S n ← S 0 (n = 1–3). Low fluorescence quantum yields in EtOH (Φfl ~ 10–4–10–3) and an increase of the Φfl values in toluene (~10–2) at room temperature and with lowering the temperature to 77 K (Φfl ~ 10–1) for a number of the compounds under study were satisfactorily explained within the framework of Marcus theory.