Improving the lifetime and the operational stability while maintaining high conductivity and mechanical flexibility is important for flexible electronic applications. In this work, we report that highly conductive and environmentally stable organic transparent electrodes (TEs) can be fabricated by laminating poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) films containing dimethyl sulfoxide and Zonyl fluorosurfactant (PDZ films) with a monolayer graphene barrier. The proposed lamination process enables graphene to be deposited onto the PDZ films uniformly and conformally with tight interfacial binding, free of wrinkles and air gaps. The graphene-laminated PDZ films exhibit an outstanding room-temperature hole mobility of ~ 85.1 cm2 V−1 s−1 since the graphene can act as an effective bypass for charge carriers. Enhanced stability of the graphene-laminated TEs under the harsh conditions is particularly promising. Furthermore, the incorporation of the graphene barrier enhances the estimated lifetime of the TEs under thermal stress by more than two orders of magnitude. This work presents that the operational and thermal stability of organic thin-films can be pursued by employing 2D carbon materials while maintaining high conductivity and mechanical flexibility.