The article discusses the traditional view of pollutant removal in water purification through catalytic oxidation, which has long been associated with degradation and mineralization pathways. However, recent studies challenge this view, revealing that organic pollutants can be removed through oxidative coupling and polymerization pathways on catalyst surfaces, known as the direct oxidative transfer process (DOTP). This process is more prevalent in heterogeneous catalytic oxidation systems using oxidants like H₂O₂ and persulfate, and catalysts such as FeOCl and Co₃O₄. The primary reaction pathways for removing organic pollutants are not degradation and mineralization, but rather coupling and polymerization, which are widespread across various heterogeneous catalytic systems. Thermodynamically, the polymerization pathway is more feasible in weakly oxidizing environments, as it requires less oxidation capability than mineralization. The misunderstanding of these pathways stems from the conventional reliance on homogeneous catalytic systems and the challenges in analyzing products and pathways in dilute solution systems. The significance of surface coupling and polymerization pathways has been underestimated for nearly a century. The identification of reaction pathways is crucial for the development of water purification technologies. Polymerization pathways offer a promising direction for future technologies, as they can reduce oxidant/energy consumption and CO₂ emissions. However, the accumulation of polymerization products on solid surfaces may lead to catalyst deactivation, necessitating future research to enhance catalyst capacity and reduce costs. The study emphasizes the importance of examining reaction pathways in catalytic oxidation systems to improve water purification efficiency.The article discusses the traditional view of pollutant removal in water purification through catalytic oxidation, which has long been associated with degradation and mineralization pathways. However, recent studies challenge this view, revealing that organic pollutants can be removed through oxidative coupling and polymerization pathways on catalyst surfaces, known as the direct oxidative transfer process (DOTP). This process is more prevalent in heterogeneous catalytic oxidation systems using oxidants like H₂O₂ and persulfate, and catalysts such as FeOCl and Co₃O₄. The primary reaction pathways for removing organic pollutants are not degradation and mineralization, but rather coupling and polymerization, which are widespread across various heterogeneous catalytic systems. Thermodynamically, the polymerization pathway is more feasible in weakly oxidizing environments, as it requires less oxidation capability than mineralization. The misunderstanding of these pathways stems from the conventional reliance on homogeneous catalytic systems and the challenges in analyzing products and pathways in dilute solution systems. The significance of surface coupling and polymerization pathways has been underestimated for nearly a century. The identification of reaction pathways is crucial for the development of water purification technologies. Polymerization pathways offer a promising direction for future technologies, as they can reduce oxidant/energy consumption and CO₂ emissions. However, the accumulation of polymerization products on solid surfaces may lead to catalyst deactivation, necessitating future research to enhance catalyst capacity and reduce costs. The study emphasizes the importance of examining reaction pathways in catalytic oxidation systems to improve water purification efficiency.