The synthesis of two new poly(dialkylstilbenevinylene)s obtained through a palladium-catalyzed polymerization with a controlled molecular weight and a terpyridine moiety in the backbone is presented. Assembly using ruthenium complexation led to coordination polymers with a ruthenium complex in the middle. The coordination homo and copolymers were characterized using NMR, UV-vis and were processed into thin films for solar cells applications. The best photoresponse was obtained for the device prepared from the ruthenium homopolymer bearing cyano substitutents with a maximum output power of 0.86 μW cm<sup>-2</sup> and a fill factor of 26% under illumination at 1000 W m<sup>-2</sup> AM1.5. A blend of this compound with a zinc porphyrin was also investigated and gave a lower performance.