The integration of graphene-based materials with metal–organic frameworks (G@MOFs) has emerged as a promising strategy for advanced wastewater treatment owing to their synergistic physicochemical properties. This review systematically compiles and critically analyzes recent advances in the synthesis, structural characterization, and application of G@MOFs for the removal of organic and inorganic micropollutants. Special emphasis is placed on how the unique combination of high surface area, tunable pore structures, and abundant active sites in G@MOFs enhances adsorption, photodegradation, and catalytic degradation mechanisms. Compared to conventional adsorbents and standalone MOFs, G@MOFs exhibit superior removal capacities, stability, and reusability. This paper also identifies key challenges in large-scale applications, regeneration, and potential environmental risks, providing a future outlook on optimizing synthesis routes and tailoring functional composites for sustainable water treatment technologies. The novelty of this review lies in providing the first dedicated, systematic evaluation of G@MOFs for wastewater micropollutant removal, integrating synthesis strategies, performance benchmarking, techno-economic aspects, environmental safety, and future application prospects into a unified framework.