We have demonstrated a direct arylation polycondensation of 3,4-ethylenedioxythiophene with 2,7-dibromo-9,9-dioctylfluorene using palladium on carbon (Pd/C) as a catalyst. Pd/C is a low-cost solid-supported palladium catalyst, giving one of the effective catalytic systems for direct arylation. The Pd/C-catalyzed direct arylation polycondensation with acetic acid/potassium carbonate in N,N-dimethylacetamide furnished a high molecular weight -conjugated alternating copolymer of EDOT-fluorene (M-n=89,300, M-w/M-n=3.27) in high yield. The polycondensation of EDOT with various dibromoarenes was also achieved, giving EDOT-carbazole, EDOT-dialylamine, and EDOT-bithiophene polymers. Optical and electrochemical properties of the polymers were also discussed. (c) 2016 Wiley Periodicals, Inc.