An electroactive polymer poly[4,7‐bis(3,6‐dihexyloxy‐thieno[3,2‐b]thiophen‐2‐yl)]‐benzo[c][1,2,5]thiadiazole is synthesized and applied as a color‐changing electrode material in supercapacitors via spray coating method. Using poly(3,4‐ethylenedioxythiophene) as the negative electrode, the all‐polymer asymmetric supercapacitors provide an energy density of 3.5–6.3 W h kg−1 and power density of 0.6–8.8 kW kg−1.