Because of its excellent catalytic activity and stability, perovskite materials are widely used in advanced oxidation processes to remove refractory organic pollutants. In this study, a series of catalysts Pr0.6Sm0.4CoxMn1‐xO3 (x = 0, 0.2, 0.4, 0.5, 0.6,0.8 and 1) with limited range effect are prepared by sol–gel method with the regulation strategy of injecting active metal Co at B site in the crystal lattice of perovskite catalyst Pr0.6Sm0.4MnO3. Under the optimal conditions, the Pr0.6Sm0.4Co0.8Mn0.2O3/PMS/RhB system showed superior catalytic performance, and the removal rate of Rhodamine B (100 mg L−1) is close to 100% within 40 min. In addition, the Pr0.6Sm0.4Co0.8Mn0.2O3 catalyst has a wider pH (2‐10) tolerance range and still has outstanding catalytic properties after multiple cycle tests. The quenching experiment and EPR test confirmed that a variety of active species are produced in the system, and the singlet oxygen as the leading path of a variety of active substances assisted to promote the efficient degradation of Rhodamine B in wastewater. This study provides a new reaction system and regulatory strategy of active structural sites for the design of Fenton‐like catalytic systems based on novel perovskite oxides.