Graphene is a rapidly rising star in materials science. This two-dimensional material exhibits unique properties, such as low resistance, excellent optical transmittance, and high mechanical and chemical stabilities. These exceptional advantages possess great promise for its potential applications in photovoltaic devices. In this Review, we present the status of graphene research for solar energy with emphasis on solar cells. Firstly, the preparation and properties of graphene are described. Secondly, applications of graphene as transparent conductive electrodes and counter electrodes are presented. Thirdly, graphene-based electron- (or hole) accepting materials for solar energy conversion are evaluated. Fourthly, the promoting effect of graphene on photovoltaic devices and the photocatalytic property of graphene–semiconductor composites are discussed. Finally, the challenges to increase the power conversion efficiency of graphene-based solar cells are explored.