In this study, a novel donor-acceptor type monomer was designed based on selenophene and benzotriazole with a bulky pendant group and synthesized through Stille coupling reaction. The monomer was polymerized electrochemically by using cyclic voltammetry and also chemically by oxidation in the presence of FeCl3. Both polymers were then compared in terms of their optical properties, electrochemical and spectroelectrochemical behaviors, kinetic and colorimetric properties and surface morphologies. Independent of the polymerization method, both electrochemically (E-PSeBTz) and chemically polymerized (C-PSeBTz) coatings showed quite similar properties. Both polymers have p-doping character and multichromic properties in their oxidized states. The polymers can be fully switched between their oxidized and neutral states in fairly short times with acceptable optical contrast at different wavelengths. Both polymers exhibit a lambda(max) of 505 nm and the optical band gaps of the materials were found to be 1.85 eV and 1.80 eV for E-PSeBTz and C-PSeBTz, respectively.