Graphene—a two-dimensional lattice oriented monolayer of sp2-hybridized carbon atoms—has taken up considerable attention leading to a growing scientific interest due to its exceptionally high electrical conductivity (orders of magnitude higher than copper), optical transparency (>90 %), chemical robustness (more than 500 °C) and mechanical stiffness (more than 1,000 GPa) as well as high specific surface area . Design and development of graphene incorporated polymer photovoltaics is one of the promising routes to harness the extraordinary properties of graphene for the generation of efficient solar-to-power conversion devices. Graphene as well as its chemically functionalized forms, graphene oxide (GO) and reduced-GO, are the smart materials for photovoltaic cells performing specific functions depending upon their intriguing properties. Herein we review the multifunctional and practical applicability of graphene and its composite materials as the electron acceptor, counter electrode and hole transport components of polymer solar cells . We conclude the chapter with the present scenario and challenges related to the stability and commercialization of graphene–polymer based photovoltaic devices .