The disinfection by-product N-nitrosodimethylamine (NDMA) is a major concern in water quality management due to its carcinogenicity. Thus, a proper pretreatment is necessary to mitigate NDMA formation upon periodic chloramination by removing precursors, such as ranitidine (RNT). This study investigated the effect of UV/sulfite pretreatment on NDMA formation from an RNT-spiked tap and chloraminated synthetic swimming pool (SSP) water. At UVC intensity of 2.1 mW cm–2 and 0.5 mM of sulfite, UV/sulfite chemistry showed complete degradation of 20 µM RNT within 30 min. It was found that SO4•– primarily reduced the NDMA formation potential (FP) of RNT, while hydrated electrons effectively mitigated the pre-formed NDMA in the SSP water. The UV/sulfite pretreatment alleviated NDMA formation during post-chloramination (24 h) by up to 82%, outperforming the commonly employed advanced oxidation processes such as UV/H2O2. However, in the presence of bromide ions, the effectiveness of UV/sulfite pretreatment was seriously deteriorated, although the bromide ion itself was found to inhibit the NDMA formation from RNT especially at pH < 8 during chloramination. Mass spectrometric analysis indicated that the NDMA-FP of RNT could be removed by UV/sulfite principally via N-methylation, dealkylation, and oxygen transfer pathways. Consequently, UV/sulfite could be used as an alternative unit process for water treatment with reduced NDMA formation.​