Thiophene functionalized polystyrene samples (TFPS) were synthesized by atom transfer radical polymerization (ATRP) of styrene, followed by Suzuki coupling with 3-thiophene (Th) boronic acid. Conducting graft polymer of TFPS with thiophene was achieved at 1.5 V in tetrabutylammonium tetrafluoroborate/dichloromethane (TBAFB/DM) by electrochemical methods. Spectroelectrochemical analysis of the resulting copolymers [P(TFPS-co-Th)] reflected electronic transitions at 449, 721 and 880 nm, revealing pi - pi* transition, polaron and bipolaron band formation, respectively. We also successfully established the utilization of dual type complementary colored polymer electrochromic devices using P(TFPS-co-Th)/poly(3,4-ethylenedioxythiophene (PEDOT) in sandwich configuration. The switching ability, stability and optical memory of the electrochromic device were investigated by UV-visible spectrophotometry and cyclic voltammetry. Device switches between brown and blue color with a switching time of 1.3 s were prepared with optical contrast (%Delta T) of 25 (c) 2005 Society of Chemical Industry.