Recent study on synthetic approaches toward polycyclic aromatic hydrocarbons (PAHs) such as graphene with a well-defined structure have attracted much attention. A research group at Ehime University has been studying the synthesis and fundamental properties of pyrrole-fused azacoronene (HPHAC), a nitrogen-containing PAH. HPHACs are composed of electron-rich pyrroles, which are easily oxidized, and their dicationic species in particular exhibit unique features such as global aromaticity based on macrocyclic π-conjugation. However, all the compounds reported so far have bulky substituents at the periphery of the HPHAC skeleton, and thus the characterization of the physical properties of the pristine HPHAC itself or the π-electron function based on π-π interactions has not been possible.