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A highly efficient and new ternary TCPP/rGO/Bi₂WO₆ Z-scheme heterojunction was designed and fabricated via a facile hydrothermal approach and a liquid ultrasonic route in sequence. The crystal structures, morphologies, microstructures, chemical compositions, elemental states, optical and photo-electrochemical properties of the heterojunction were characterized. This Z-scheme TCPP/rGO/Bi₂WO₆ photocatalyst has significantly enhanced photocatalytic activity for the tetracycline (TC) degradation under the irradiation of visible light (λ > 420 nm) within 60 min, as compared to pure Bi₂WO₆, rGO/Bi₂WO₆ and TCPP/Bi₂WO₆ composites. The effects of the photocatalyst dosages, pollutant concentrations, coexisting ions and illumination conditions on the photodegradation were investigated. According to the trapping experiments and electron spin resonance analyses, the hole (h⁺) and superoxide radical …