We have recently reported a series of pyrrole-fused azacoronenes. Due to the interior nitrogen atoms and various resonance forms, all azacoronenes showed multiple oxidation states with different electronic properties. On the basis of these results, a pyrrole-fused azacoronene functionalized with carbonyl groups was designed and synthesized. From the ESR and crystal structure analyses, the azacoronenes revealed spin-delocalized diradical nature in the neutral state. The CV results showed multistep oxidation and reduction peaks. The band gap is very small and the absorption spectra tailed near-infrared region. Pi-extended systems over the previous azacoronenes were also obtained using a similar synthetic strategy. Some crystal structure analyses revealed highly contorted structures. In the presentation, we will report the synthesis, structures, and basic physical properties.