This paper presents the results of PAH determination adsorbed on fine and ultrafine particles emitted to the air from diesel exhaust, with a special emphasis on sample preparation procedure prior to HPLC-FL analysis. Samples were taken with a personal environmental monitor and personal cascade impactor in order to ensure size-segregated sampling of air particulate matter (in the range of the following particles’ diameters <0.25, 0.25-0.5, 0.5-1.0, 1.0-2.5, and 2.5-10 μm). Application of solid phase extraction with a BakerBond PolarPlus column and mixture of acetonitrile/isopropanol (1:1 v/v) for PAH’s elution ensures recovery values of 94%. The mean content of total PAHs collected at the Diesel engine came to (68.0±3.4) and (78.1±3.9) ng·m^-3 in PM_2.5 and PM₁₀ fractions, respectively. The sum of pyrene, fluoranthene, and benzo(a)anthracene contributed to 74% in the PM_2.5 and 66% in PM₁₀ fraction of total PAH content. Average total PAH’s concentrations in smaller fractions of 0.5-1.0 μm, 0.25-0.5 μm, and <0.25 μm separated with PCI sampler were determined at the level of (15.5±0.7), (2.05±0.1), and (40.9±2.1) ng·m^-3, respectively. In the ultrafine particles’ fraction (diameters below 0.25 μm), such compounds as phenanthrene, fluoranthene, pyrene, benzo(a)anthracene, benzo(k)fluoranhene, and benzo(ghi)perylene were identified and determined. The percentage of PAH’s input in PM_0.25 fraction came to the level of 52% on average, in comparison to total PAH concentrations in the PM₁₀ fraction.