1,4-benzodioxan-based polydithienylpyrrole (PBDO) is electrochemically synthesized. Cyclic voltammograms are acquired to examine the redox properties of the PBDO films at various scan rates. Spectroelectrochemical and colorimetric studies are also conducted. The PBDO homopolymer has a bandgap of 2.38 eV and displays yellowish-green to bluish-violet coloration upon doping. Electrochromic devices (ECDs) that employ PBDO as an anodic polymer and poly(3,4-(2,2-diethylpropylenedioxy)thiophene) (PProDOT-Et 2 ) (or poly(3,4-ethylenedioxythiophene) (PEDOT)) as a cathodic polymer are constructed. The PBDO/PProDOT-Et 2 ECD shows higher T max (32.3%) and coloration efficiency (η, 437.5 cm 2 C −1 ) at 586 nm than those of PBDO/PEDOT ECD ( T max = 20.2%, η = 152.0 cm 2 C −1 at 606 nm). The PBDO/PEDOT and PBDO/PProDOT-Et 2 ECDs show satisfactory optical memories and redox stability.In the last two decades, π-conjugated polymers such as carbazole, triphenylamine (TPA), thiophene-based materials, and their derivatives have attracted considerable interest because of their widespread use in artificial muscles, 1 smart windows, 2 electrochromic devices (ECDs), 3-6 light-emitting diodes, 7-9 catalyst supports, 10-12 photovoltaics, 13,14 and fluorescence sensors. 15-17 Applications of π-conjugated polymers in the fields of electrochromic materials and energy-saving smart windows have attracted widespread attention in both academic and industrial communities. The various types of electrochromic materials may be divided into two general classes: inorganic electrochromic materials (transition metal oxides) and organic electrochromic materials (conducting polymers and viologens). π-conjugated polymers as eletrochromic materials have attracted attention because of their outstanding advantages over transition metal oxides, such as long-term stability, high optical contrast ratio, fast response time, high coloration efficiency, 18 low switching potential, and broad color availability through fine-tuning of their bandgap via modifications of their chemical structures. 19 The design and synthesis of new π-conjugated polymers and improvement of their switching ability are issues currently being investigated by researchers.The π-conjugated polymers used in electrochromic materials are mainly polyaniline (PANI), 20 polypyrrole (PPy), 21 polythiophene (PT), 21 polycarbazole, 22 polytriphenylamine, 23 and poly(3,4-ethylenedioxythiophene) (PEDOT). 24 Among these electrochromic conjugated polymers, PTs have been dominant due to their high conductivity, good redox reversibility, swift change of color with potential, and environmental stability. 25 Recently, various strategies have been proposed to fine-tune the colored neutral state of PTs. 26 PEDOT, an important PT derivative, contains two electron-donating oxygen atoms on the 3,4-positions of thiophene. PEDOT is usually used as a cathodically coloring material in ECDs. Poly(2,5-dithienylpyrrole) (PSNS) derivatives are also potential PT derivatives due to their low oxidation potential and facile che...