Efficient synthesis of a library of novel benzopyrido[1,4]oxazepinones was accomplished by Cs₂CO₃-mediated one-pot coupling of N-substituted-o-chloronicotinamides and o-halogenated phenols using cuprous oxide catalysis in DMF at 120 °C through an O-heteroarylation-Smiles rearrangement-cyclization cascade (16 examples). The C–N bond construction process is biased in favour of Smiles rearrangement allowing regioselective generation of these tricyclic molecular architectures essentially free from Goldberg-N-arylation products in good to excellent yields.