A novel alkoxy-bridged dithieno (3, 2-B:2',3'-D) pyrrole (DTP) derivative was synthesized and its corresponding polymer poly(1,2-bis(2-(4H-dithieno[3,2-b:2',3'-d]pyrrol-4-yl)ethoxy)ethane) (P(DTP-alkoxy-DTP)) was successfully obtained electrochemically. The effects of alkoxy bridge in the structure on the electrochemical and spectroelectrochemical properties of the polymer were also investigated in detail. The results showed that the polymer film exhibits multielectrochromic behavior and a low band gap of 1.82 eV.