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The removal of water pollutants by photocatalysis is a promising technique, mainly due to its environmentally friendly and sustainable nature. In this study, the degradation of a recalcitrant organic pollutant, malachite green (MG), was investigated in water by a microstructured silver oxide photocatalyst. The silver oxide (Ag₂O) microparticles (MPs) were synthesized by a low-cost, green method, mediated by green tea leaves extract. The surface, morphological and optical properties of the synthesized Ag₂O MPs were determined by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, X-ray diffraction (XRD) analysis, Fourier transform infrared (FTIR) spectroscopy, and ultraviolet-visible (UV-visible) spectrophotometry. The synthesized Ag₂O MPs showed good photoactivity, represented by 83% degradation of malachite green (MG) ([C]₀ = 0.4 mM, Ag₂O loading = 0.1 g L⁻¹) at neutral pH, in 3 h. Persulfate ions (PS) showed a strong synergistic effect on the efficiency of solar/Ag₂O photocatalysis, represented by complete MG removal in 15 min, in the presence of 1.6 mM PS. The results revealed that solar/Ag₂O, particularly solar/Ag₂O/PS photocatalysis is a promising method for the elimination of toxic organic pollutants, such as malachite green, from the water environment.