This study has tested and optimized different filter media and pre-conditioning methods, extraction methodologies, cleaning techniques and solvents, concentration procedures and GC-MS parameters in order to establish the best methodology to sample and analyze particle-bound PAH collected in low volume samples (1.4 m³). The procedure developed combines the use of quartz fiber filters pre-conditioned at 400 °C for 48 h with a simple extraction procedure and optimized GC-MS parameters. The average method detection limits ranged from 4 to 15 pg m⁻³ for the 4–7 ring PAHs, precision (RSD) ranged from 0.3 to 9.7% and accuracy ranged from −6 to 25%. This method was validated with the extraction and analysis of the Standard Reference Material 1649a and was tested successfully on samples collected in outdoor microenvironments proving suitable for determination of particle-bound PAH concentrations without interferences in low volume samples.