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. Co-monomer selection and backbone functionalization substantially modifies the polymer MO energies, thin film morphology, and charge transport properties, as indicated by electrochemistry, optical spectroscopy, X-ray diffraction, AFM, DFT calculations, and TFT response. When polymer P7 is used as an OPV acceptor with PTB7 as a donor, the corresponding blend yields TFTs with ambipolar mobilities of μe = 5.1 × 10−3 cm2 V–1 s–1 and μh = 3.9 × 10−3 cm2 V–1 s–1 in ambient, among the highest mobilities reported to date for all-polymer bulk heterojunction TFTs, and all-polymer solar cells with a power conversion efficiency (PCE) of 1.70%, the highest reported PCE to date for an NDI-polymer acceptor system. The stable transport characteristics in ambient and promising solar cell performance make NDI-type materials promising acceptors for all-polymer solar cell applications.