A centrosymmetric polymer precursor, 4-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)butan-1-amine (TPBA), was synthesized via a Knorr–Paal reaction and its copolymer with EDOT was electrochemically synthesized and characterized. While P(TPBA) has only two colors in its oxidized and neutral states, its copolymer with EDOT has eight different colors. Electrochromic devices based on P(TPBA)/PEDOT and P(TPBA-co-EDOT)/PEDOT were constructed and characterized. The oxidized state of the device shows blue color whereas it shows purple for the reduced state. At moderate potentials the device has good transparency with green and gray colors. The maximum contrast and switching time of the multielectrochromic copolymer device were measured as 25% and 0.8 s at 575 nm. Copolymerization not only increases the polymer’s color scheme, but also improves its properties, such as redox stability and switching time.