Quinoline derivatives are promising materials for optoelectronic and biomedical applications. A simple and scalable aza-Diels-Alder reaction of imine, napthyl alkyne was described for the synthesis of various chloroquinoline derivatives, benzoquinolines, and corresponding polybenzoquinolines. The exploitation of quinoline derivatives with different functionalities demonstrates the great potential not only for organic electronics but also for the molecular transformation for a board range of researchers.