Kanechlor-300, -400, -500 and -600, Phenoclor DP-3, -4, -5 and -6 and Sovol mixtures were analyzed for their chlorobiphenyl (CB) composition using high-resolution one-dimensional and multidimensional gas chromatography-electron capture detection (MDGC-ECD) techniques. The congener patterns of tested Kanechlor and Phenoclor mixtures resembled Aroclor 1016, 1242, 1254 and 1260. However, differences in the percentage contribution of minor constituents were noticed among these mixtures, which could be due to variations in the boiling-point fractionation of these commercial products. CB pattern of Sovol was different from the rest of the mixtures tested. It showed a composition in between ca. 30%, 40%, 50% and 60% overall chlorine levels. MDGC-ECD study showed the presence of hitherto unnoticed non-CB compounds coeluting with CBs in some commercial PCBs. The use of these mixtures as quantitation standards should be considered with caution. CB patterns of Sovol and a water extract of the Gulf of Finland matched closely, indicating a point source contamination to these waters.