A high-yielding method for the synthesis of 3-arylbenzo[4,5]thieno[3,2- b]pyrroles has been developed via pyrrole ring annulation to the aromatic benzo[ b]thiophene system, using 3-arylazirines as a N‒C=C synthon. The reaction is catalyzed by Ni(hfacac) 2 and proceeds through the azirine ring opening across the N=C3 bond. Azirines with both electron-donating and electron-withdrawing C3-aryl substituents tolerate the reaction conditions. The reaction of the N-methylindole analog also provides the annulation product but in moderate yield. The described synthesis is the first example of a dealkoxycarbonylative annulation reaction, in which 2 H-azirines act as the annulation reagent.