The conditions in programmable temperature vaporization inlet of a gas chromatographymass spectrometry (PTV-GC-MS) were optimized to enhance the detection of five compounds of polycyclic aromatic hydrocarbon (PAH) namely acenaphthylene, fluorene, anthracene, phenanthrene and pyrene. PTV parameters such as injection volume, vent pressure, vent time, vent flow, initial heating rate, purge flow rate, purge time and injection delay time were optimized. The optimized injection volume was 150 µL, which was introduced into the inlet by six times repeating injection of 25 µL using automatic liquid sampler at an interval of 5 seconds between each injection. The optimized vent flow and pressure are 400 mL/min and 5 psi for 2 minutes, respectively. The purge flow rate and initial heating rate were optimized to 400 mL/min for 2 minutes and 400 o C/min. The performance of PTV solvent vent mode was compared to the splitless injection mode. The obtained limit of detection (LOD) in solvent vent mode was approximately five to six times lower than the limit obtained in splitless injection mode. The determined recoveries varied from 98.1 to 98.9% with pooled relative standard deviations ranging from 9.8 to 11.4%.