Carbon dots, emerging as novel photoluminescent nanomaterials, have attracted increasing attention for photocatalytic applications such as hydrogen evolution, carbon dioxide reduction, pollutant degradation and organic synthesis. However, the separation of carbon dots from the reaction system is always a cumbersome process, which may limit their applications in photocatalysis. Herein, we report the synthesis of a graphene quantum dot with CO₂-switchable reversible phase transfer performance via a facile surface functionalization approach. The mechanism of this hydrophilicity and hydrophobicity alteration involves the protonation–deprotonation transformation and reversible formation of hydrophilic bicarbonate salts when CO₂ is bubbled and removed. Then, the obtained graphene quantum dot was utilized as a visible-light photocatalyst for the oxidative coupling of amines. Our photocatalyst demonstrates excellent catalytic efficiency with both high reaction conversion and selectivity. Furthermore, the proposed graphene quantum dot could be recycled via a simple CO₂ bubbling method.