Owing to the structural importance and synthetic value of quinazoline and quinazolinone scaffolds in drug discovery, we herein report a novel NH 4I‑involved oxidative coupling of readily available 2,1‑benzisoxazoles/isatoic anhydrides with benzylic alcohols for the selective synthesis of these heterocycles. In this three‑component transformation, ammonium iodide served as both an economical nitrogen source and a co-oxidant, avoiding the use of additional additives. Importantly, this metal- and additive-free protocol enables precise cleavage of C−O/N−O bonds with simultaneous formation of C–N bonds in a single operation, exhibiting excellent chemoselectivity, atom economy and broad functional group tolerance. Furthermore, the resulting quinazoline and quinazolinone derivatives were efficiently transformed into high‑value analogues of bioactive molecules, underscoring the synthetic utility of the method.