Herein, we report a nickel-catalyzed intramolecular dual annulation reaction of alkyl nitrile-containing 1,2,3-benzotriazin-4(3H)-ones to synthesize polycyclic quinazolinones. This catalytic reaction can construct the core structure of polycyclic quinazolinone alkaloids; therefore, we also apply this reaction as the critical step to access fifteen relevant alkaloids to demonstrate efficacy.