As a widely used substrate for flexible electronics, indium‐tin oxide‐based polymer electrodes (polymer‐ITO electrodes) exhibit poorly visible light transmittance of less than 80%. The inferior transmittance for polymer‐ITO electrodes severely limits the performance improvement of polymer‐ITO based electronics. Here, a conceptually different approach of the double‐sided antireflection coatings (DARCs) strategy is proposed to modulate both the air–polymer substrate interface and ITO–air interface refractive index gradient, to synergistically improve the transmittance of polymer‐ITO electrodes. On the basis of SiO2 nanoparticles antireflection layer on polymer substrate, a polymer–metal oxide composite antireflection film is fabricated on the ITO side. Resultantly, the transmittance of ITO‐based flexible electrodes is successfully improved from 76.8% to 89.8%, which is the highest transmittance among the reported ITO‐based flexible electrodes. Furthermore, the photoluminescence emission intensity of luminescent materials enveloped with the DARCs electrodes increases by 74% over that with reference electrodes, demonstrating the DARCs antireflection strategy can efficiently improve the performance of flexible optoelectronic devices. With DARCs electrode, the flexible perovskite solar cells exhibit an enhanced efficiency from 18.80% to 20.85%.