Chloramphenicol (CAP) is of great concern due to its extensive use and nonnegligible impact on the eco-environment. Herein, the degradation performance and mechanism of CAP by UV/sulfite advanced reduction processes (ARPs) were systematically investigated. 90.67 % degradation efficiency and 92.22 % dechlorination of CAP were simultaneously achieved within 50 min using UV/sulfite-ARPs. The degradation and dechlorination efficiency of the CAP remained elevated with the increase of sulfite concentration, and eventually complete degradation and dechlorination were achieved. Hydrated electrons (eaq−) and direct UV photolysis dominated in the degradation and dechlorination of CAP at pH 5–11. The presence of commonly co-existing anions, humic acid and various water matrices exhibited negligible effect on the CAP degradation and dechlorination efficiencies. Possible degradation pathways of CAP were proposed. Ecotoxicity prediction and seed germination experiments indicated that the acute and chronic ecotoxicity of CAP solution was significantly reduced after the treatment with UV/sulfite-ARPs. Overall, this study demonstrated that UV/sulfite-ARPs could be a promising approach for the CAP purification from wastewaters.