The United Kingdom is used as a study area in which to examine (i) the relationship between primary and potential secondary emissions of PCDD/Fs; (ii) the balance between atmospheric emissions and deposition; and (iii) the contemporary environmental burden of PCDD/Fs and possible historical input profiles. This critical review exercise is seen as an important aid to identifying gaps in knowledge and research needs and directing a scientifically sound strategy for PCDD/F risk reduction. The paper focuses on two key compartments, air and soil, as these play an important role in the movement and storage of PCDD/Fs. The terrestrial agricultural food chain supplies the majority of human exposure to PCDD/Fs via the pathway air−deposition−crop/pasture/soil−grazing animals−meat/dairy products−human diet. Primary emissions of PCDD/Fs to the atmosphere are expected to decline in the future following the implementation of new legislative controls. This should be reflected by a further decline in ambient air concentrations, as our calculations indicate that primary emissions are currently the main PCDD/F sources to air. The soil burden will take much longer to decline, due to the extreme persistence of these compounds in this environmental matrix. The paper highlights uncertainties and future research needs concerning the environmental sources, fate, and behavior of this group of compounds.