Heteroatom-containg polycyclic hydrocarbons have attracted a great deal of attention from materials science, since such heteroatoms can tune the electronic nature without modifying the structure. Given these expectations, we have reported a novel nitrogen-containing π-system, i.e. hexapyrrolohexaazacoronene and its derivaticves. To further understand the structure–property relationship, we have newly designed and synthesized pyrrole-fused azacoronenes with curved structure. In the presentation, we will report on the synthesis, crystal structures, and optical and electronic properties in neutral and oxidized states.