Advances in the research of graphene in the development of optoelectronic devices have clearly witnessed a strong increase in the past few years. Graphene, a zero bandgap semiconducting material exhibits exceptional properties such as high conductivity, mechanical robustness, optical transparency, flexibility and much more yet to be discovered. Due to its extraordinary properties, graphene is believed to have the potential to replace many traditional electrode materials that are being used in optoelectronic devices. To achieve a high device performance various deposition techniques have been developed to deposit a thin, transparent, and uniform layer of graphene on different substrates. However, the success of these methods strongly relies on the processing conditions, resulting morphology and the work function of the graphene films. This review summarizes the developments in the synthesis and deposition methods of graphene electrodes in combination with organic solar cells over the past 10 years.