The synthesis of, two new poly(thienylene vinylene) derivatives is described, i e poly(3 octyl-2,5 thienylene vinylene) (O-PTV) and poly(bis[octylpheny1-2,5 thienylene vinylene]) (BOP-PTV) Both polymers have been prepared via the dithiocarbamate (DTC) precursor route The polymerization protocol of the monomer toward the precursor polymer has been optimized by the use of different bases, leading to improved reproducibility of the polymerization step Processability has been guaranteed by the introduction of alkyl side chains Finally the precursor polymers were converted toward conjugated polymers and they were fully characterized by UV/vis, IR, GPC and cyclic voltammetry Bulk heterojunction solar cells with PCBM as acceptor showed promising power conversion efficiencies of 0 80% for BOP PTV and 0 92% for O-PTV