A naphthalenediimide (NDI)-based conjugated polymer was synthesized by a two-step direct C-H arylation sequence. In the first step, two ethylenedioxythiophene units were coupled to NDI by direct arylation. In the second step, the direct arylation polycondensation of the monomer, formed in the first step, with 2,7-dibromo-9,9-dioctylfluorene afforded the corresponding NDI-based conjugated polymer (PEDOTNDIF) with molecular weight of 21,500 in 91% yield. The optical and electrochemical properties of the polymer were evaluated. The polymer showed ambipolar behavior in organic field-effect transistors (OFETs). The electron mobility of PEDOTNDIF was estimated to be 2.3 x 10(-6) cm(2) V-1 s(-1) using an OFET device with source-drain (S-D) Au electrodes. A modified OFET device with S-D MgAg electrodes increased the electron mobility for PEDOTNDIF to 1.0 x 10(-5) cm(2) V-1 s(-1) due to the more suitable work function of these electrodes, which reduced the injection barrier to the semiconducting polymer. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1401-1407