AbstractA new synthetic route to novel ruthenium‐containing polymers is reported. [Ru(L)(L′)Cl2] type complexes (L and L′ = bidentate N^N ligands) with a dibromo‐substituted ligand were polymerized by Stille cross‐coupling reaction. The subsequent displacement of chloride ligands by thiocyanate was highly effective and the structures of the target polymers were fully characterized. The main chain absorption showed a significantly red‐shift upon metal coordination and the metal‐to‐ligand charge transfer (MLCT) band of the complex enhanced the photon harvesting ability of the polymer. The extent of π‐electron delocalization of the ancillary ligands also showed interesting effects on the electronic properties of the polymers. The photosensitizing and bandgap tuning properties of these Ru(II) complexes demonstrated a new avenue to develop new classes of optoelectronic materials.