The Fe(III)-S(IV) system used for advanced oxidation processes (AOPs) at acidic pH has just been proposed and demonstrated valid for very few contaminants in the last several years. In this work, we investigated the effect of ultraviolet A (UVA) radiation on the degradation efficiency of the Fe(III)/S(IV) system at near-neutral pH. Paracetamol (PARA) was selected as a model con-taminant. The influencing factors, such as initial pH and Fe(III)/S(IV) molar ratio on chemical kinetics, and the mechanism of PARA degradation are investigated, with an emphasis on the de-termination of dominant oxidant species. Our results show that irradiation enhances the PARA degradation by accelerating the decrease of pH to acidic levels, and the optimal pH for the deg-radation of PARA in the Fe(III)/S(IV)/O2 system was around 4.0. At near-neutral pH, more than 60% of PARA was decomposed within 40 min under irradiation, whereas no significant degrada-tion of PARA was observed using Fe(III)/S(IV) at pH 7.0 without irradiation. Mechanism inves-tigation revealed that sulfate radical (SO4•‒) is the main oxidant species generated and responsi-ble for the PARA degradation under these conditions. This finding may have promising impli-cations in developing a new degradation process for dealing with wastewater at near-neutral pH by the Fe(III)/S(IV)/O2 system under UVA irradiation.