A new efficient synthetic method toward processable bis-N-annulated quaterrylene from easily available N-annulated perylene derivatives, which is conducted by DDQ/Sc(OTf)(3) oxidative coupling and ring fusion, is reported. In light of the good processability and the strong electron-donating ability, which is evidenced from the low oxidative potentials, bis-N-annulated quaterrylene is very promising for use as functional components in molecular devices.