Innovations in water technology are needed to solve challenges of climate change, resource shortages, emerging contaminants, urbanization, sustainable development and demographic changes. In particular, conventional techniques of wastewater treatment are limited by the presence of poorly biodegradable organic matter. Alternatively, recent Fenton, Fenton-like and hybrid processes appear successful for cleaning of different types of liquid wastewaters. Here, we review the application of metallic catalyst-H₂O₂ systems in the heterogeneous Fenton process. Each metallic catalyst-H₂O₂ system has unique redox properties due to metal oxidation state. Solution pH is a major influencing factor. Catalysts made of iron and cerium form stable complexes with oxidation products and H₂O₂, thus resulting in reduced activities. Copper forms transitory complexes with oxidation products, but copper catalytic activity is restored during the reaction. Silver and manganese do not form complexes. The catalyst performance for degradation and mineralization decreases in the order: manganese, copper, iron, silver, cerium, yet the easiness of practical application decreases in the order: copper, manganese, iron, silver, cerium.