Human subpopulations experience different exposure to persistent organic pollutants (POPs) because of differences in the structure of their food webs and the extent of environmental contamination. Here we quantify the time-variant exposure of different human populations around the world to one representative POP, namely the polychlorinated biphenyl (PCB) congener 153, based on a dynamic simulation of both global environmental fate (using the model BETR-Global) and human food chain bioaccumulation (using the model ACC-HUMAN). The approach identifies subpopulations whose diets include a carnivorous mammal as experiencing the world's highest PCB-153 exposure, i.e. the very large biomagnification potential of their food web more than makes up for the remoteness of their living environment. However, for subpopulations that do not eat warm-blooded carnivores, the proximity to sources of PCBs is more important than food web structure and environmental conditions for differentiating their exposure to PCBs.