Synthesis of a new thiophene-based monomer; 5,12-dihydrothieno[3',4':2,3][1,4]dioxocino[6,7-b]quinoxaline (DDQ), was realized. The chemical structure of the monomer was characterized by H-1 NMR, FTIR and mass spectroscopy techniques. Electrochemical polymerization of DDQ and characterization of the resulting polymer [P(DDQ)] was performed. Moreover, the spectroelectrochemical and electrochromic properties of the polymer film were investigated. P(DDQ) has a low oxidation potential (0.9 V) and low band gap (1.73 eV) compared to polythiophene. In addition, dual-type polymer electrochromic device (ECD) based on P(DDQ) with poly(3,4-ethylenedioxythiophene) (PEDOT) was constructed. Spectroelectrochemistry, electrochromic switching, stability and open-circuit stability of the device were studied. It was observed that polymer have good switching time, reasonable contrast and optical memory. (c) 2007 Elsevier Ltd. All rights reserved.