Due to its unique atom-thick 2D structure and remarkable physicochemical properties, graphene has been making a profound impact in many areas of science and technology. In particular, a great deal of recent attention has been attracted to explore graphene and its derivatives for photoelectrochemical applications, with the potential to harness graphene's excellent properties for opening up new opportunities in next generation photoelectrochemical systems. Over the past few years, much work has been done in the design and preparation of novel graphene-based materials for a wide range of applications in photoelectrochemistry, ranging from photoelectrochemical solar cells, photocatalytic decomposition of organic pollutants, photocatalytic splitting of H2O, photocatalytic conversion for fuels, and so on. In this review article, we summarize the state of research on graphene-based materials from the standpoint of photoelectrochemistry. The prospects and further developments in this exciting field of graphene-based materials are also discussed.