A simple synthetic route to hard-to-prepare polycyclic (hetero)aromatic compounds with the [1,2,5]chalcogenodiazolo[3,4-b]pyrazine scaffold was developed based on the intramolecular nucleophilic aromatic hydrogen substitution reaction. Electrochemical and photophysical measurements demonstrated that the synthesized polycyclic systems can be considered as narrow-bandgap (from 1.25 to 1.44 eV) n-type organic semiconductors, the energy levels of which are comparable to those of commercially available electronic semiconductors.