A novel and efficient rhodium- and copper-co-catalyzed C–H bond activation and annulation for the construction of bioactively important quinazolines has been developed. This [4 + 2] annulation strategy utilizing alkyl azides as the carbon–heteroatom synthons shows high efficiency in the synthesis of six-membered benzoheterocycles containing two heteroatoms. This aerobic oxidative protocol provides a useful application of simple alkyl azides in N-heterocycle synthesis with N2 and H2O as byproducts.