Abstract The capillary gas chromatography of polychlorinated biphenyls (PCBs) is reviewed. Focus is on the most recent developments in the separation and detection of PCBs rather than sample preparation methods. Included are a comprehensive look at stationary phases that have been used to separate PCBs and the relatively new work on chiral separations of PCBs. Mass spectrometry and atomic emission are presented as selective detection techniques. Suggestions for additional research are proposed where appropriate.