In this report, we highlight the synthesis and optical and electrochromic properties of dibenzothiophen-S,S-dioxide and 3-hexylthiophene based polymers. For this purpose a novel dibenzothiophen-S,S-dioxide and 3-hexylthiophene bearing, donor-acceptor-donor type monomer (THSO(2)) was synthesized through Stille cross-coupling reaction. THSO(2) was electrochemically polymerized in tetrabutylammonium hexafluorophosphate- dichloromethane couple. Furthermore, THSO(2) was subjected to electrochemical copolymerization in the presence of 3-hexylthiophene both potentiodynamically and potentiostatically. The resulting homopolymer and copolymers were characterized by means of cyclic voltammetry, FTIR, spectroelectrochemistry and kinetic studies. Depending on the synthesis conditions, the polymers exhibited optical band gaps ranging from 2.23 to 2.60 eV. Moreover, a highly soluble, fluorescent homopolymer was achieved using FeCl(3) as the oxidant. The polymer provides several properties to be used in organic electronic applications. (C) 2011 Elsevier B.V. All rights reserved.