A simple and accurate method for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in thermoplastic elastomer by gas chromatography-mass spectrometry (GC-MS) has been developed. The effects of various operational parameters (e. g. sample pretreatment, extraction solvent, extraction method, extraction temperature, extraction time, etc) on the extraction efficiency were carefully investigated by analyzing different kinds of positive PAHs thermoplastic elastomer samples made by the manufacturer. The samples were extracted ultrasonically with toluene, concentrated to about 1 mL and then redissolved by cyclohexane. After being purified by dimethyl sulfoxide liquid-liquid extraction, 16 PAHs in the sample were analyzed by GC-MS and quantified by internal standard method. Different kinds of thermoplastic elastomer materials and products were analyzed by this method with the recoveries ranged from 70% to 117% and the relative standard derivations between 0.2% and 10.8%. The method is acceptable for the determination of PAHs in thermoplastic elastomer materials and products.