The global energy shortage and environmental degradation are two major issues of concern in today’s society. The production of renewable energy and the treatment of pollutants are currently the mainstream research directions in the field of photocatalysis. In addition, over the last decade or so, graphene (GR) has been widely used in photocatalysis due to its unique physical and chemical properties, such as its large light-absorption range, high adsorption capacity, large specific surface area, and excellent electronic conductivity. Here, we first introduce the unique properties of graphene, such as its high specific surface area, chemical stability, etc. Then, the basic principles of photocatalytic hydrolysis, pollutant degradation, and the photocatalytic reduction of CO2 are summarized. We then give an overview of the optimization strategies for graphene-based photocatalysis and the latest advances in its application. Finally, we present challenges and perspectives for graphene-based applications in this field in light of recent developments.