A method of gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-MS/MS) has been optimized for the determination of polycyclic aromatic hydrocarbons (PAHs) in air samples. In the analysis step, isotope dilution was introduced to the quantification of PAHs. The GC-MS/MS method was applied to the analysis of the real air samples around a big petrochemical power plant in South China. The results were compared with those obtained by gas chromatography coupled to mass spectrometry (GC-MS). The results showed that better selectivity and sensitivity were obtained by GC-MS/MS. It was found that the external standard of deuterated-PAHs and internal standard of hexamethyl benzene were disturbed seriously with GC-MS, and the problems were both solved effectively by GC-MS/MS. Therefore more accurate quantification results of PAHs were obtained with GC-MS/MS. For the analysis of real samples, the RSDs of relative response factors ranged from 2.60% to 15.6% in standard curves; the recoveries of deuterated-PAHs ranged from 55.2% to 82.3%; the recoveries of spiked samples ranged from 98.9% to 111%; the RSDs of parallel specimens ranged from 6.50% to 18.4%; the concentrations of field blank samples ranged from not detected to 44.3 pg/m3; and the concentrations of library blank samples ranged from not detected to 36.5 pg/m3. The study indicated that the application of GC-MS/MS on the analysis of PAHs in air samples was recommended.