A sensitive method for the quantification of brominated polycyclic aromatic hydrocarbons (BrPAHs) in environmental samples is yet to be developed. Here, we optimized the analytical conditions for liquid chromatography tandem mass spectrometry with atmospheric pressure photoionization and post-column infusion of dopant (LC-DA-APPI-MS/MS). We then compared the sensitivity of our developed method with that of conventional gas chromatography high-resolution MS (GC-HRMS) by comparing the limits of quantification (LOQs) for a range of BrPAHs. Finally, to evaluate our developed method, 12 BrPAHs in sediments and fish collected from Tokyo Bay, Japan, were analyzed; 9 common PAHs were also targeted. The LOQs of the developed analytical method were 14 – 160 times lower than those of GC-HRMS for the targeted BrPAHs. The developed analytical method is a sensitive approach for determining the concentrations of BrPAHs in sediment and fish samples.