In this presentation we will describe the design rationale, synthesis, characterization, of several organic semiconducting polymers for printed thin-film transistors (TFTs), photovoltaic cells (OPVs), and batteries as well as understand their charge-transport characteristics as a function of the polymer architectural parameters (MW, PD, regioregularity, nanostructure, synthetic methodology) and device structure/interface modifications. particularly, we show how regioregularity and side functionalization in naphthalenediimide polymers affect polymer aggregation in solution and in the solid state as well as device performance. Our work enable the realization of fully printed organic TFTs with electron mobilities > 3 cm2/Vs, highly efficient and stable batteries, OPV cell with efficiencies >10%.