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Graphene is emerging as one of the most useful electrode materials for various organic optoelectronic devices because of its outstanding properties such as high optical transparency, excellent mechanical flexibility, good electrical conductivity, and environmental stability. Numerous synthesis and transfer techniques used to obtain large‐area and high‐quality graphene materials are demonstrated, aiming at high‐performance graphene‐based organic optoelectronic devices such as solar cells, light‐emitting diodes, and field‐effect transistors. The properties, synthesis, and transfer processes of graphene are first introduced. Recent research progress on organic optoelectronic devices with graphene bottom, top, and full electrodes is then reviewed. Finally, graphene composite electrodes integrated with other conductive materials are also summarized. All these advanced works represent important steps in the evolution of graphene electrodes and indicate a bright future for their application in organic optoelectronic devices. [ABSTRACT FROM AUTHOR]