Large amounts of wastewater containing refractory organics would be produced in chemical, pharmaceutical and other industries. This kind of wastewater has complex composition and high toxicity, which has become a puzzle in the field of industrial water treatment. Recent years, electro-Fenton(EF) technology has attracted much attention due to its efficient removal ability towards organic pollutants. However, traditional EF technology still has some shortcomings such as low solubility of iron ions at neutral condition, slow reduction rate of Fe³⁺ and insufficient hydrogen peroxide production. Fortunately, the problems mentioned above can be effectively fixed by different enhancing methods like adding organic or inorganic ligands, synergistic effects of transition metals, as well as heteroatom-modified carbon materials, enhancing the effect of electro-Fenton technology. This review briefly introduces some latest work focused on the enhancement of EF process via different co-catalysis methods and analyzes their main mechanism. The advantages and disadvantages of typical co-catalysts are compared and analyzed. The main development direction in preparation and application is prospected according to the problems like insufficient mechanism research, complex synthesis process and that single technology cannot give full play to its advantages. This article aims to provide a reference for enhancing the EF removal of refractory organics by co-catalyst.