Chiral polychlorinated biphenyls (PCBs) 45, 84, 88, 91, 95, 132, 136, 139, 149, 171, 183 and 196 were separated each in its two enantiomers by cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC). Mixtures of β- and γ-cyclodextrins were used as chiral modifiers in a 2-(N-cyclohexylamino)ethanesulphonic acid (CHES) buffer containing urea and sodium dodecyl sulphate (SDS) micelles. Separations of multicomponent mixtures of PCBs into their enantiomers were also performed. A mixture of PCBs 45, 88, 91, 95, 136, 139, 149 and 196 was separated into all sixteen enantiomers in an analysis time of approx. 35 min.