Mono-ortho and non-ortho coplanar polychlorinated biphenyls (PCBs) were analyzed in Aroclors, seals, and humans by graphitized carbon, a recently developed HPLC method (Hong et al. 1992b) and high-resolution gas chromatography with electron capture detection (HRGC/ECD). The concentration data were multiplied by potency factors derived from aryl hydrocarbon hydroxylase (AHH) induction to give 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents. The ability to separate coplanar PCBs from the majority of PCBs has allowed the use of TCDD toxicity equivalence to compare the relative dioxin-like potency of PCB residues in the complex mixtures. The most active mixtures, Aroclors 1254, 1248, and 1242, contained 42-54% by weight of chlorine. The results demonstrate that the apparent dioxin-like potency of PCB residues in Aroclors, seals, and humans is dominated by three congeners, 3,3',4,4'-tetra-, 2,3,3'-4,4'-, and 3,3',4,4',5-pentachlorobiphenyl (IUPAC nos. 77, 105, 126).