The elution order of 209 polychlorinated biphenyls (PCBs) was determined using five types commercially available capillary columns (VF-Xms, Rtx-20, VF-35ms, VF-1301ms and VF-200ms). In addition, the interference among molecular ion peaks PCDDs non-dioxin like PCB congeners, which affect during dioxin analysis by GC/MS, clarified.