<p>The advanced oxidation process provides significant advancements in the field of environmental remediation all around the world. In this context, various photocatalysts with different light-sensitive capabilities were engineered and employed for improved photocatalytic performance. Recently, the development of 2D-layered photocatalysts has attracted significant attention due to their tremendous pollutant removal efficiencies. The current review explicitly explains the recent developments in graphene and their derivatives-based heterojunction for enhanced photodecomposition behavior for water purification and detoxification. It will provide a systematic roadmap to develop advanced graphene-based nanocomposite for future technologies. In addition, the review highlights the different synthesis strategies, properties, charge transfer mechanisms, and optimized parameters for different graphene-based photocatalysts. The insight perspective and the future possibilities from the recent reports on graphene, graphene oxide (GO), and reduced graphene oxide (RGO) have been presented here, which provides the potential to enhance their photodecomposition efficiency for water purification further. A comprehensive view of the different graphene-based heterostructures such as plasmonic nanocomposites, semiconductor nanocomposites, transition metal dichalcogenides (TMDCs)-based nanocomposites, and organic molecules-based photocatalyst and their underlying charge transfer mechanism have been presented. Finally, a summary and future perspective of the development of graphene-based photocatalysts has been mentioned and elaborated. The advancement of photocatalytic systems, integration with graphene-based nanostructures, and innovative technologies for large-scale implementation are poised to offer solutions to energy and environmental challenges in the foreseeable future.</p> Graphical Abstract <p></p>