Polyquinolines have been studied since the early 1970s due to their favorable chemical, optical, electrical, and mechanical properties. However, surprisingly few synthetic strategies have been developed for the preparation of these polymers. Herein, we demonstrate the application of the aza-DielsAlder (Povarov) reaction for the synthesis of soluble polyquinolines from a bifunctional monomer. Our approach furnishes polyquinolines with a unique architecture and connectivity in only two synthetic steps from inexpensive, commercially available reagents. The reported strategy may therefore represent a welcome addition to the polymer chemists toolkit by providing ready access to a diverse library of polyquinoline-type materials.