The facile assembly of polyaryl-substituted azafluoranthenes via CoBr2/dppp-catalyzed [2+2+2] cycloaddition with 1,6-diynes and nitriles are demonstrated here. This method show high efficiency, mild conditions, low cost, and wide substrate scope. Furthermore, the fluorescent spectra of selected azafluoranthenes indicate that this kind of skeleton might show good photophysical properties and have good potential in material science.