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Removal of toxic organics and bacterial disinfection are important tasks in wastewater treatment. Most heavy metal-based catalysts for degradation of aqueous organic pollutants in heterogeneous Fenton-like processes suffer from the toxicity of leached metals. The present work reports environmentally benign systems for both degradation of organics and bacterial disinfection. Calcium substituted LaFeO 3- δ perovskite was demonstrated as an efficient catalyst to activate peroxymonosulfate (PMS) for degradation of phenol, methylene blue and rhodamine 6 G. Compared to LaFeO 3- δ and nanocrystal Fe 3 O 4 , the lattice oxygen vacancies in B-site cation-deficient perovskite of La 0.8 Ca 0.2 Fe 0.94 O 3 - δ (LaCaFeO 3- δ ) particles renders this material a greatly improved catalytic performance. Electron paramagnetic resonance (EPR) suggested that both sulfate (SO 4 –) and hydroxyl radicals ( OH) played critical roles in the advanced oxidation processes. Moreover, silver doped perovskite (Ag-LaCaFeO 3- δ )/PMS successfully inhibited the growth of waterborne pathogen Escherichia coli and Methicillin-resistant Staphylococcus aureus (MRSA) at a lower dose than silver ions, proving a synergetic effect between free radicals and Ag + in killing the bacteria. Therefore, Ag-LaCaFeO 3- δ /PMS would be promising for practical wastewater treatment. [ABSTRACT FROM AUTHOR]