To achieve excellent activation efficiency of peroxymonosulfate (PMS), this work prepared a biochar-supported CuO (CuO@BC) catalyst, and the CuO@BC/PMS system was proposed to remove the organic matter in natural surface water and reduce the fouling of ultrafiltration membrane. The successful synthesis of CuO@BC was demonstrated through characterization of its microscopic morphology and chemical composition by various techniques. The prepared heterogeneous catalyst showed a strong catalytic effect on PMS, which significantly removed natural organic matter through the production of active substances (•OH, SO4•−, O2•− and 1O2) from water. With respective degradation rates of 39.4% and 59.4%, the concentrations of DOC and UV254 dropped to 1.702 mg/L and 0.026 cm−1, respectively. Additionally, the CuO@BC/PMS oxidation displayed potent oxidation capabilities for contaminants and fluorescent organics with various molecular weights. The system effectively decreased the amount of organic matter that caused reversible and irreversible fouling of polyethersulfone membranes in natural water by 85.8% and 56.3%, respectively. The main fouling mechanisms changed as well, with standard and complete blocking dominating the entire filtration process. The results demonstrated the capacity of the CuO@BC/PMS system to remove contaminants in natural water and mitigate membrane fouling.