We describe the development of a liquid chromatography with negative-ion atmospheric pressure photoionization tandem mass spectrometric (LC/NI-APPI/MS/MS) method for the simultaneous determination of tetrabromobisphenol A (TBBP-A) and five polybrominated diphenyl ethers (BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154) in water. A mobile phase methanol/acetone/water was used, where acetone acts also as dopant. NI-APPI produced precursor ions corresponding to [M?H]? for TBBP-A, [M?Br+O]?, and [M?2Br+O]? for the BDE congeners studied. Each compound was quantified operating in multiple reaction monitoring mode. Linearity was observed in the range 0.025–10 ng injected for all compounds. Coefficients of determination R2 ranged from0.9934 to 0.9982. BDEswere poorly retained by solid-phase extraction (SPE) from river water and sewage treatment plant effluent, thus liquid–liquid extraction (LLE) by n-hexane should be used for these samples. The recoveries of TBBP-A and PBDEs from tap water (SPE), river water and industrial wastewater (LLE) were in the range of 81–88%, 78–92%, and 43–99%, respectively, with relative standard deviations below 17%. The limits of detection, based on signal-to-noise ratio of 3, ranged from 0.004 to 0.1 ng injected, and method quantification limits were 0.2–3.3 ng L?1 but BDE47 (20.3 ng L?1). Only TBBP-A was found in a treated industrial sewage at 4 ng L?1, while BDE-99 and BDE-100 were detected on suspended solids.