A methodology based on microwave-assisted extraction (MAE) and LC with fluorescence detection (FLD) was investigated for the efficient determination of 15 polycyclic aromatic hydrocarbons (PAHs) regarded as priority pollutants by the US Environmental Protection Agency and dibenzo(a,l)pyrene in atmospheric particulate samples. PAHs were successfully extracted from real outdoor particulate matter (PM) samples with recoveries ranging from 81.4 +/- 8.8 to 112.0 +/- 1.1%, for all the compounds except for naphthalene (62.3 +/- 18.0%) and anthracene (67.3 +/- 5.7%), under the optimum MAE conditions (30.0 mL of ACN for 20 min at 110 degrees C). No clean-up steps were necessary prior to LC analysis. LOQs ranging from 0.0054 ng/m(3 )for benzo(a)anthracene to 0.089 ng/m(3) for naphthalene were reached. The validated MAE methodology was applied to the determination of PAHs from a set of real world PM samples collected in Oporto (north of Portugal). The sum of particulate-bound PAHs in outdoor PM ranged from 2.5 and 28 ng/m(3).