▎ 摘　　要

The rise in global demand for green chemistry and sustainable development have driven immense research in the fundamental science of catalysis. Metal-free catalysis, serves as an ideal industrial technology, has emerged as a new frontier and hot point in modern catalysis science due to its green and sustainable properties. As a new carbonaceous material, graphene exhibits high surface area, excellent stability, unique mechanical and electronic properties. Its physical and chemical properties can be further modulated by modification and functionalization. Graphene derivatives have been successfully employed in a variety of chemical transformations recently, showing them to be promising metal-free organocatalysts. This review highlights the recent advancements of graphene-derived materials as metal-free carbocatalysts and their application in organic reactions, such as oxidation, reduction or hydrogenation, coupling, substitution, etc. The possible structure-performance relationships of graphene-based carbocatalysts and metal-free organocatalytic mechanisms are also emphasized.