Past and current polychlorinated biphenyl (PCB) inputs to the environment, mainly in industrialized countries, continue to determine a global re-distribution of these contaminants. In order to better understand PCB transport and distribution phenomena, a number of large-scale distribution studies have been recently published in the literature. In this paper a nationwide survey of 28 pine needle samples taken across the UK is presented. Mean PCB concentrations of a number of latitudinal bands (transects) revealed the presence of a decreasing concentration gradient from southern England to northern Scotland of a factor of 7. The pine needle data also provide evidence to suggest: 1) that there has been a decrease in the PCB concentration of the atmosphere in the southern UK; and 2) there is a relationship between regional mean needle PCB concentrations and population densities. Calculated air concentrations from the pine needle results were compared with measured literature data of a similar area to test the possibility of using bioconcentration factors (BCF) based on n-octanol: air partition coefficients (Koa) to predict air-leaf equilibrium of semivolatile organic compounds. A more detailed analysis, in accordance with some literature data, has revealed that uncertainties arise when leaf-air uptake of molecules with high Koa values (Log Koa > 8–9) is modelled.