An accelerated solvent extraction (ASE) method has been developed for the determination of polycyclic aromatic hydrocarbons (PAHs) present in both atmospheric particulate and gaseous phases in this study. Extraction parameters such as the combination of solvents, extraction temperature, and static extraction time were investigated and optimized. Effective extraction was achieved using a 3:1 mixture of n-hexane and acetone as extraction solvents at 100 oC in 30 min for all the compounds studied. The optimized extraction method was compared with conventional extraction methods and validated using NIST certified SRM 1649a. The recoveries obtained for certified 12 PAHs were in the range of 82-126% with relative standard deviation between 6 and 28%. The validated ASE technique was used followed by GC-MS analysis for the determination of PAHs distributed between gaseous and particulate phases in the atmosphere of Singapore. Total average concentrations of PAHs in air samples were 33.54 ± 19.32 ng m-3, with 4.72 ± 2.80 ng m-3 in particulate phase and 28.82 ± 16.92 ng m-3 in gaseous phase, respectively. The results obtained from this study are compared to those reported from other areas of the world.