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The formation of brominated disinfection byproducts (Br-DBPs), which are generally significantly more cytotoxic and genotoxic than their chlorinated analogues, in chloramination has not been fully examined. In this work, the formation of new polar Br-DBPs in simulated drinking waters was examined using state-of-the-art ultraperformance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry. As many as 29 aliphatic, aromatic, or nitrogenous polar Br-DBPs were detected in chloramination, and five of them (including 2,4,6-tribromoresorcinol, 2,6-dibromo-4-nitrophenol, 2,2,4-tribromo-5-hydroxy-4-cyclopentene-1,3-dione, 2,2,4-dibromochloro-5-hydroxy-4-cyclopentene-1,3-dione, and 2,2,4-bromodichloro-5-hydroxy-4-cyclopentene-1,3-dione) were tentatively identified. Unlike chlorination, chloramination favored the formation of aromatic and nitrogenous polar Br-DBPs and was mild enough to allow polar intermediate Br-DBPs to accumulate. To further explore the formation mechanism of Br-DBPs in chloramination, a quantitative empirical model involving 33 major reactions was developed to describe the overall kinetics. According to the modeling results, bromochloramine and monobromamine were the major species responsible for 54.2–58.1% and 41.7–45.7%, respectively, of the formed Br-DBPs, while hypobromous acid accounted for only 0.2% of the formed Br-DBPs; direct reactions between monochloramine and natural organic matter accounted for the majority of the formed chlorinated DBPs (93.7–95.1%); hypochlorous acid and hypobromous acid in the chloramination were at ng/L or subng/L levels, which were not enough to cause polar intermediate Br-DBPs to decompose.