AbstractReactive oxygen species (ROS) containing sulfate and hydroxyl radicals can act as Fenton type reagents to remove organic contaminants from water. Here, a catalytic system silver metavanadate is reported for the activation of peroxodisulfate in an aqueous medium to generate ROS, which is further utilized for the efficient degradation of the water‐soluble pollutants such as phenols, pesticides, antibiotics, and organic dyes. Remarkably, complete carbon mineralization of the water‐soluble contaminants is achieved to form carbon dioxide as the major product. In‐situ electron paramagnetic resonance (EPR) studies combined with ex‐situ methods reveal that a massive amount of hydroxyl radicals (•OH) are formed through sulfate radical anions (SO4•−) and act as the ROS for the organic pollutant degradation. In addition, the stability of the catalyst is monitored by various characterization techniques.