The normal method to determine the trace brominated flame retardants such as polybrominated biphenyls (PBBs) and polybrominated diphenylethers (PBDEs) contained in the electronic and electrical products is gas chromatography/mass spectrometry (GC/MS). However, the method is based on the determinations of the persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs), and polychlorinated naphthalene (PCNs) etc. The interferences of those compounds are inevitable. Therefore, in order to overcome this problem, two methods e.g. 1) The combination use of gas chromatography negative ion chemical ionization mass spectrometry (GC-NICI-MS) and gas chromatography-electron impact-mass spectrometry (GC-EI-MS) is employed, 2) a matrix solid-phase dispersion (MSPD) method with YMC ODS-C18 as carrier is developed. The result show that, by the former method, the brominated isomers or ramifications are distinguished remarkably from other halogen compounds because that anion fragment retention peaks of ［Br］-, ［HBr2］- and molecule chain fragment retention peaks of ［M+2］+，［M+4］+，［M+6］+，［M+8］+ are observed simultaneously, and thus the selectivity to determine bromine-containing retardant flames is greatly improved. Using the latter method, the gas chromatographic peaks of multiple polychlorinated biphenyls and polybrominated diphenylethers can be efficiently separated. Thus provides a project to solve interferences of POPs in brominated flame retardants’ determinations. The standard addition experimental results of 10 kinds of BDEs/PCBs belonging to 8 sorts of electronic and electrical equipment show this method has a high precision and reliability due to 60%～98% recovery and <9.5% relative error, which meet the needs regulated by the IEC Commission. It provides a technical support for electronic and eletrical industries in China to further comply with RoHS directive.