Display omitted •Cu-doped LaFeO3 was studied as catalyst for Fenton-degradation of organics.•It was much more effective in degrading organic compared with undoped LaFeO3.•The mechanism for photo-Fenton degradation was studied.•Its application was optimized in terms of solution pH, H2O2 and catalyst dosage.•The excellent stability and reusability suggested its potential for practical use. Cu-doped LaFeO3 was prepared by a facile hydrothermal reaction and evaluated as highly efficient photo-Fenton-like catalyst under visible light for organic degradation. The use of LFO-15Cu (LaFe0.85Cu0.15O3), which possessed favourable physicochemical characteristics, could achieve almost complete decolourisation of cation and anion dyes within 60min visible light irradiation. The mechanism study by ESR spectroscopy confirmed LFO-15Cu could activate H2O2 under visible light to generate many more hydroxyl radicals than LFO (LaFeO3). LFO-15Cu was proven with excellent stability and reusability; and in turn showed great potential for use in continuous photo-Fenton-like degradation of organic in water under visible light.