Soils are a major reservoir of organic pollutants, and soil–air partitioning and exchange are key processes controlling the regional fate of pollutants. Here, we report and discuss the soil concentrations of polycyclic aromatic hydrocarbons (PAHs), their soil fugacities, the soil–air partition coefficients (KSA) and soil–air gradients for rural and semirural soils, in background areas of N-NE Spain and N-NW England. Different sampling campaigns were carried out to assess seasonal variability and differences between sampling sites. KSA values were dependent on soil temperature and soil organic quantity and type. Soil fugacities of phenanthrene and its alkyl homologues were 1–2 orders of magnitude higher than their ambient air fugacities for all sampling sites and periods. The soil to air fugacity ratio was correlated with soil temperature and soil redox potential. Similar trends for other PAHs were found but with lower fugacity ratios. The ubiquitous source of PAHs from background soils to the atmosphere found in all temperate regions in different seasons provides an indirect evidence of potential in situ generation of two to four ring PAHs and their alkyl homologues in the surface soil. We discuss this hypothetical biogenic source and other potential processes that could drive the high soil to air fugacity ratios of some PAHs.