Capillary gas chromatography with atomic emission detection (GC-AED) was evaluated for the analysis of polychlorinated biphenyls (PCBs). Since Cl-responses were almost independent of the PCB structure, individual PCBs were quantitated with an accuracy better than 10% utilizing a Cl-calibration plot based on a single randomly selected congener (universal calibration). In addition, within a 5-10% accuracy, GC-AED enabled estimation of total PCB residue levels and calculation of the percentage by weight of chlorine in contaminating PCB mixtures. Thus, although PCB detection limits were higher with GC-AED than with GC-ECD, the former technique was very attractive for PCB investigations and enabled significant simplification of PCB quantitation.