The composition of polychlorinated biphenyl (PCB) congeners in serum samples is compared between a cohort previously exposed to PCBs from working at a capacitor plant (n=180) and a cohort of Great Lakes sport-caught fish eaters (n=217). Fourteen congeners were measured in both samples. A multiple logistic regression model differentiating the two groups as a function of relative proportions amongst congeners 74, 138, 153, 180, and 201 correctly classifies more than 99% of the people (395/397); higher proportions of congeners 74, 153, and 201 characterize capacitor plant workers, while higher proportions of congeners 138 and 180 characterize fish eaters. The pattern is driven by the relative amounts of 74+153+201 compared to 138+180; all of the fish eaters, but only 5% of the capacitor plant workers, have a greater percent of 138+180 than 74+153+201. Consideration of combinations of congener levels and their relative proportions is relevant to tracking route of exposure and may also be relevant to modeling effects on health outcomes.