Pyrazine-fused 1,2,6,6a-tetrazapentalenes (PyTeAP) are zwitterionic tricyclic compounds exhibiting an original pattern with four consecutive nitrogen atoms. They were obtained by a challenging cyclization through the formation of a N–N bond under thermolytic conditions. Ten derivatives were synthesized, and the original scaffold of PyTeAP was confirmed by single-crystal X-ray diffraction analysis of one derivative. Examination of their photophysical properties in solution revealed blue fluorescence with λem = 416–426 nm. Theoretical investigations of the aromaticity in these compounds through magnetic criteria evidenced the presence of a dominant 14-electron circuit at the periphery.