AbstractA new neutral green electrochromic (EC) polymer, namely poly(5,8‐bis(2,3‐dihydro[3,4‐B][1,4]dioxin‐5‐yl)‐2,3‐dual(4‐(hexadecyloxy) phenyl) quinoxaline) (PBOPEQ) was designed and synthesized. PBOPEQ‐poly(3,4‐ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) film was further prepared by electrochemical polymerization on the PEDOT:PSS modified indium tin oxide (ITO) electrode. Scanning electron microscopy images and ultrasonic experiment indicate that PBOPEQ‐PEDOT:PSS film shows better film‐forming ability and stronger interface adhesive with ITO electrode compared to that of PBOPEQ film. It is worth mentioning that PBOPEQ‐PEDOT:PSS film presents more reversible redox characteristic, better optical contrast (~40%) and coloration efficiency (~230 cm2 C−1) at 678 nm, excellent EC stability and memory property (36 hr), which should be ascribed to that the electroactive PEDOT:PSS layer facilitates the charge transfer process and enhances the ion doping/dedoping properties. EC device based on PBOPEQ‐PEDOT:PSS film exhibits superior integrated performance such as reversible color change from green to transmissive, optical contrast of 41.0% and switching time less than 1 s. Accordingly, PBOPEQ‐PEDOT:PSS is an excellent EC material when combined with electroactive PEDOT:PSS interface layer for achieving high performance device, which shows potential applications in displays, electronic papers, and tags.