Gas chromatographic separations of chlorobiphenyls, alkylbiphenyls and alkylchlorobiphenyls were carried out at 200° on glass capillary columns coated with OV-101, Carbowax 20M and Apiezon L as stationary phases. Apiezon L was the most suitable phase for this purpose, in terms of separation, reproducibility of retention indices and reliability of structure-retention correlations for the prediction of indices. Compounds in the mixtures were identified by comparison with reference materials analyzed under similar conditions, by structure-retention correlations and by combined gas chromatography-mass spectrometry. Quantitative analysis of a mixture of polychlorinated biphenyls was performed by using the internal standard method, taking into account experimentally determined flame ionization detector response factors. The results, obtained on stationary phases with different polarities, can be used as an additional tool for qualitative analysis.