The exploration of efficient heterogeneous catalysts for persistent organic pollutant removal is extremely attractive. In the present work, MnO₂/Mn₃O₄ photo-Fenton catalysts were designed by a facile hydrothermal route to activate peroxymonosulfate (PMS) under visible light irradiation for organic pollutant degradation. The optimized MnO₂/Mn₃O₄ heterojunction shows excellent Rhodamine B (RhB) removal efficiency, whose apparent kinetic constant is 11.9 and 5.36 times as high as the MnO₂ and Mn₃O₄. Meanwhile, there is a neglectable attenuation in catalytic performance after 5 recycling runs. Based on the active species trapping experiments, the non-radical process contributes more than the radical process during RhB degradation. Moreover, factors including the dosage of PMS, initial RhB concentration, initial pH, the presence of various anions, different organic pollutants, and water sources are investigated. Systematical characterizations reveal that the enlarged specific surface areas and the efficient charge separation aroused from the Z-scheme mechanism are attributed to the enhanced photo-Fenton performance. The present work contributes to the construction of the Mn-based photo-Fenton catalyst with efficient PMS activation capacity for environmental remediation.