Under a small project, one-year-old Scots Pine needles collected from 25 spatially distant sites were examined in monitoring the extent of environmental diffusion and possible sources of polychlorinated biphenyls (PCBs) in ambient air, their depositions and uptake by plants in Poland. The congener-specific determination of planar and non-planar chlorobiphenyls was achieved by isotope dilution HRGC-HRMS method after a highly refined extraction on multi-layer column of silica gel and alumina layer and clean-up, and fractionations, followed by Hypercarb-HPLC and PYE-HPLC sub-fractionation steps. Contents of 117 chlorobiphenyls determined in pine needles varied for the 25 sites studied and is between 2.7 and 49 ng/g wet weight. The PCBs pollution and congener-specific composition of pine needles to some degree varied according to the site or region surveyed depending on population density and industrialization. Many of the country-side areas showed lower concentrations between 2.7 and 8.9 ng/g ww. Pine needles in areas close to well populated and industrial regions of Opole, Kutno, Włocławek and Dębica showed the highest PCB pollution with concentrations varying between 30 and 49 ng/g ww. The Kutno site showed the highest pollution and this fact probably can be explained by possible emission from transformer manufactures located at some distance west of the Kutno area. Factor analysis (FA) and depending on the site revealed on relationship of PCBs composition of pine needles both with highly chlorinated PCB constituents of the mixtures such as Chlorofen, Aroclor 1254, Aroclor 1268 and Sovol but also of lower chlorinated PCB constituents of Aroclor 1242, Aroclor 1248, Clophen A40 or Delor 103. Thermal processes were considered a less significant source of PCBs in ambient air over Poland compared to evaporative sources related to technical PCB formulations. Supplemental materials are available for this article. Go to the publisher's online edition of Journal of Environmental Science and Health: Part A to view the free supplemental file.