Based on the realization of efficient utilization of cotton stalk lignin, the degradation of cotton stalk lignin by a CDs/CuO synergistic emulsion system was investigated. Copper oxide (CuO) nanoparticles with monoclinic crystal structure were prepared and carbon dots (CDs) synthesized by microwave method was combined with CuO. Under visible light, water and n-butanol were used to construct a water–oil (W/O) emulsion reaction system to achieved depolymerisation of lignin into small molecule compounds. The involvement of hydrogen peroxide (H2O2) makes the degradation of lignin in this system even more effective. The final high value-added monophenolic compound of 57.70 mg g−1 was obtained, among which the most abundant were six monophenolic compounds such as vanillin, eugenol and vinyl guaiacol and so on. The results of GC-MS and FTIR characterization indicated that H-type monomers were the main products of lignin degradation in this system. The process conditions for lignin hydrogenolysis in this system were optimized and the best ratio of CDs/CuO was obtained by product analysis. There were characterized by SEM, TEM, XRD, XPS, FTIR, and US–vis. The results show that CDs/CuO aggregates into flower clusters, in which CDs are uniformly distributed on the surface of rhomboidal CuO monoliths. The analysis shows that the doping of CDs improves the absorption efficiency of CuO in the visible region, while reducing the complexation of CuO photogenerated electrons and holes, which achieves the purpose of improved photocatalytic activity of CuO.