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In this work, Ag₂CO₃ was prepared via a solution-based method and was further characterized by XRD, Raman spectroscopy, SEM/EDS analysis, and UV-VIS spectroscopy. SEM results revealed the formation of micro-sized particles with a rectangular shape. The photocatalytic activity of the catalyst was evaluated in the degradation of 4-tert-butylphenol (4-t-BP) under simulated solar light irradiation. The effects of 4-t-BP initial concentration (2.5–10 ppm), catalyst dosage (100–300 mg/L), different types of lamp sources, and water matrix were investigated. Complete 4-t-BP (5 ppm) degradation was achieved after 60 min by Ag₂CO₃ (200 mg/L). The effect of anions such as CO₃²⁻, HCO₃⁻, NO₃⁻, and Cl^- in the concentration range of 100–300 mg/L was also studied. CO₃²⁻ promoted the photocatalytic degradation process, while HCO₃⁻ and NO₃⁻ exhibited an inhibition effect, which was marked with increasing HCO₃⁻ and NO₃⁻ concentrations. The presence of Cl⁻ at the concentration of 100 mg/L increased 4-t-BP degradation, but higher concentrations inhibited the photocatalytic reaction. Cyclic experiments showed that the catalyst practically retained its catalytic activity toward 4-t-BP degradation after three successive experimental runs.