A Cu/Ag-catalyzed annulation of 3-aryl-2H-azirines with anthranils has been developed to expedite syntheses of (quinazolin2-yl)methanone derivatives. The transformation represents an unprecedented approach which employs a copper catalysis to cleave both a N-C2 azirine bond and N-O anthranil bond. Subsequently, an unexplored 1,3-hydroxyl migration and β-N elimination are likely the key to access (quinazolin-2-yl)methanone derivatives.