ABSTRACT This study applied ultraviolet/peroxymonosulfate (UV/PMS) and UV/hydrogen peroxide (UV/H2O2) processes to the advanced treatment of membrane bioreactor (MBR) effluent. The degradation efficiency of refractory organic matter and the reaction mechanisms of the two processes were systematically investigated. The results showed that the degradation efficiency of the UV/PMS processes was significantly lower than that of the UV/H2O2 process when the PMS concentration was significantly lower than the H2O2 concentration, e.g. the UV254 removals under optimal conditions were 72.92% and 82.21%, respectively. Additionally, the UV/PMS process could operate over a broader pH range. The degradation efficiency of the UV/PMS process was slightly increased by HCO3 – and Cl- due to the activation of PMS, while in the UV/H2O2 process, HCO3 - and Cl- depressed the degradation efficiency by competing with organic matter to react with reactive oxygen species (ROS). After the two processes, the aromaticity, humification, condensation degree, and molecular weight of refractory organic matter in the MBR effluent were considerably decreased. Fulvic- (HA) and humic-like substances (FA) were greatly degraded by the two processes. The UV/PMS had a superior degradation efficiency for macromolecular HA in the early stage of the reaction, and the UV/H2O2 could degrade HA to protein-like substances in the latter stage of the reaction. These differences between the two processes could be attributed to the dominance of different ROS, with SO4 •- and HO• dominating in the UV/PMS, and HO• dominating in the UV/H2O2. The results of this study provide theoretical support for the application of MBR effluent treatment.