Electro-Fenton (EF) process has received much attention among the various advanced oxidation process, due to its higher contaminant removal and mineralization efficiencies, simplicity in operation, in situ generation of hydrogen peroxide, etc. Heterogeneous EF process rectifies some of the drawbacks of conventional EF process by using solid catalyst for the generation of reactive hydroxyl radicals in water medium. The efficiency of various heterogeneous EF catalysts such as iron oxides, pyrite, iron supported on zeolite, carbon, alginate beads, etc. was tested by various researchers. All of these catalysts are insoluble in water; and most of them are stable and reusable in nature. Depending on the iron leaching characteristics, hydroxyl radicals are generated either in the solution or over the catalyst surface. Catalysts with higher leaching characteristics exhibit the first radical generation mechanism, while the stable catalyst with insignificant leaching exhibits the second radical generation mechanism. Adsorption of the pollutant over the surface of the catalyst also enhances the pollutant degradation. Overall, heterogeneous EF process is very potent, powerful, and useful for the pollutant decontamination from the water medium.