Abstract Polycyclic aromatic hydrocarbons (PAH) from ambient air particulate matter (PM) were analyzed by a new method that utilized direct immersion (DI) and cold fiber (CF) SPME-GC/MS. Experimental design was used to optimize the conditions of extraction by DI-CF-SPME with a 100 μm polydimethylsiloxane (PDMS) fiber. The optimal conditions included a 5 min equilibration at 70 °C time in an ultrasonic bath with an extraction time of 60 min. The optimized method was validated by the analysis of a NIST standard reference material (SRM), 1649b urban dust. The results obtained were in good agreement with certified values. PAH recoveries for reference materials were between 88 and 98%, with a relative standard deviation ranging from 5 to 17%. Detection limits (LOD) varied from 0.02 to 1.16 ng and the quantification limits (LOQ) varied from 0.05 to 3.86 ng. The optimized and validated method was applied to the determination of PAH from real particulate matter (PM10) and total suspended particulate (TPS) samples collected on quartz fiber filters with high volume samplers.