Novel vinylogous tetrathiafulvalene (TTF) containing polymers (13 and 14) were prepared by the oxidative dimerization polymerization of bisdithiafulvenes. The obtained polymers were soluble in common organic solvents such as CHCl3. The structures of the polymers were confirmed by H-1 NMR and cyclic voltammetry analysis. The number-average molecular weights of 13 and 14 were estimated from gel permeation chromatography to be 3600 and 3800, respectively. Through the introduction of phenylene or phenylene-vinylene spacers, distortion between dialkoxybenzene and vinylogous TTF units was effectively prevented according to ultraviolet-visible analysis. The polymers exhibited a strong electron-donating property investigated by cyclic voltammetry analysis. Chemical doping by CF3SO3H gave doped polymers having a cationic radical and a dication of a vinylogous TTF unit. (c) 2006 Wiley Periodicals, Inc.