Bis-periazulene (cyclohepta[def]fluorene), which is an unknown pyrene isomer, was synthesized as kinetically protected forms. Its triaryl derivatives 1c-e exhibited the superimposed electronic structures of peripheral, polarized, and open-shell π-conjugated systems. In contrast to previous theoretical predictions, bis-periazulene derivatives were in the singlet ground state. Changing an aryl group controlled the energy gap between the lowest singlet-triplet states.