OLED/OPV tandem devices have attracted great interest due to their various functions in green technology and potential sensing applications. Here we report a novel concept to improve the luminous efficiency and energy conversion efficiency of tandem bifunctional devices by integrating antireflection structures consisting of irregular nanopillars as the capping layer. The nanopillars were made on flexible polycarbonate substrates by using a nanoimprint method with an anodized aluminum oxide template. The average reflectivity of the patterned polycarbonate substrate at visible wavelengths was reduced to 3.3%. With the antireflection structures, the luminous intensity for bifunctional devices was improved by 41.9% compared to a device with a flat capping layer. The power conversion efficiency was improved from 0.48% to 0.61%, a 27.0% enhancement at normal incidence.