Poly(arylenevinylene)s constitute an important class of π-conjugated polymers for their potential utility as optoelectronic materials. Herein, we developed a sequence of rhodium-catalyzed stitching polymerization of 1,2-dialkynyl-(hetero)arenes and aromatization-driven alkene isomerization for the synthesis of new poly(arylenevinylene)s. The polymerization and subsequent alkene isomerization proceeded smoothly with high degree of stitching efficiency by employing a Rh/tfb complex as the catalyst, and not only diynes but also triynes and tetraynes could be polymerized to give poly(arylenevinylene)s that are not easily accessible by existing synthetic methods. The polymers obtained by the present method were thermally stable, and their optical properties could be varied depending on the repeating unit structure.