Polyquinolines have been studied since the early 1970s due to their favorable chemical, optical, electrical, and mechanical properties. These materials have shown particular promise for applications in organic optoelectronic devices due to their impressive stabilities. However, there are few synthetic strategies available for the preparation of polyquinolines, including transition metal catalyzed Suzuki and Sonogashira couplings, oxidative polymerizations, and the Friedlander synthesis. We have developed a new synthetic route to polyquinolines based on the aza-Diels–Alder (Povarov) reaction. Our approach furnishes polyquinolines with a unique architecture and connectivity in only two synthetic steps from inexpensive, commercially available reagents. The properties of the resulting products have been extensively characterized with chromatographic, spectroscopic, and electrochemical techniques. Our scalable synthetic strategy provides ready access to a diverse library of polyquinoline-type materials.