Polycyclic aromatic compounds possessing heteroatoms are one of the most important materials for organic electronics. Because of the lack of a suitable synthetic methodology, only a few polycyclic aromatic compounds with ring junction heteroatoms, heteroatom-doped nanographenes, have been synthesized to date, even though theoretical investigations have suggested that those molecules are attractive not only as the electronic materials but also as substructures of heteroatom-doped nanocarbons. Herein, we describe development of novel tandem hetero-Friedel-Crafts reactions and their application for the synthesis of heteroatom-fused polycyclic aromatic compounds. These compounds showed strong luminescence or carrier transport ability, thus can be a promissing class of organic materials for optelectronic devices. We have demonstrated their potential utility by fablicating phosphorescent organic light-emitting diodes with a sufficiently high efficiency and a long device lifetime.