The electrochemical polymerization of the 3,3″-di[(S)-(+)-2-methylbutyl]-2,2′:5′,2″-terthiophene (DMBTT) monomer was carried out potentiodynamically on indium tin oxide (ITO), Pt or glassy carbon (GC) electrodes in anhydrous CH3CN with TBAPF6 as supporting electrolyte. Films with good adhesion were obtained for all the tested substrates and they were characterized by various analytical techniques including UV–Vis–NIR absorption spectroscopy, cyclic voltammetry (CV), scanning electron microscopy (SEM), and gel permeation chromatography (GPC). The most outstanding properties of the electrochemically synthesized polymer were compared with those of the same polymer obtained by a chemical method. The film obtained on ITO displayed a reversible electrochromic behavior under potential switching between −0.50 and +1.00V vs. SCE.