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π-conjugated polymers based on the electron-neutral alkoxy-functionalized thienyl-vinylene (TVTOEt)building-block co-polymerized,with either BDT (benzodithiophene) or T2 (dithiophene) donor blocks,or NDI (naphthalenediimide) as an acceptor block,are synthesized and characterized.The effect of BDT and NDI substituents (alkyl vs alkoxy or linear vs branched) on the polymer performance in organic thin film transistors (OTFTs) and all-polymer organic photovoltaic (OPV) cells is reported.