In recent years, 2D–2D layered heterojunctions have emerged as promising photocatalytic platforms for the sustainable destruction of refractory pollutants because of their distinct advantages. Herein, we have rationally synthesized an organic–inorganic g-C3N4/WS2 heterojunction, with intimate interfacial contact, via a facile hydrothermal-driven self-assembling approach. Systematic investigations involving electrochemical impedance spectroscopy measurements and Mott–Schottky analysis reveal that the internal electric field between g-C3N4 and WS2 induces a Z-scheme charge transfer mechanism. Under visible light irradiation, the optimized photocatalyst exhibits a high degradation efficiencytowards two broad-spectrum antibiotics, i.e., tetracycline (TC) (89%) and sulfamethoxazole (SMX) (97%), with the apparent reaction rate constants several folds higher than that of bulk g-C3N4 and pristine WS2 nanosheets. Further, the g-C3N4/WS2 photocatalyst exhibits a favorable reusability of four operation cycles. Additionally, the impacts of different reaction variables are explored and the probable routes of photocatalytic dissociation of TC and SMX by g-C3N4/WS2 are proposed. The present findings not only validate the feasibility of g-C3N4/WS2 to eliminate consumer-derived micropollutants from the aqueous phase without creating secondary pollutants but also provide important insights for designing highly efficient 2D material-based heterojunction photocatalysts for decentralized wastewater treatment.