Utilizing seawater for toilet flushing is an effective way to conserve freshwater in coastal cities. During chlorination for disinfecting saline wastewater effluents, the high levels of bromide from seawater are oxidized to hypobromous acid which may then react with effluent organics to form brominated disinfection byproducts (DBPs). In this research, by applying a new precursor ion scan method, we detected and identified a group of halopyrroles in a chlorinated saline wastewater effluent, including tetrabromopyrrole, tribromochloropyrrole, tribromoiodopyrrole, and tribromopyrrole, with tetrabromopyrrole as the predominant species. It is the first time that this group of halopyrroles were identified as wastewater DBPs (though 2,3,5-tribromopyrrole has been found to be a DBP in drinking water before). Detection of halopyrroles was problematic as these compounds in the pretreated samples were found to convert to halonitropyrroles; the problem was successfully solved by diluting the pretreated samples. The formation, occurrence, precursor, and toxicity of tetrabromopyrrole were investigated. This DBP showed significantly higher developmental toxicity than any of the haloaliphatic and haloaromatic DBPs previously tested.