Polycyclic aromatic hydrocarbons (PAHs) including isomeric pairs were separated in capillary electrokinetic chromatography using a cationic surfactant cetylpyridinium bromide (CPBr) as additive. With addition of 2 mM CPBr into the running electrolyte, dynamic coating occurs in the capillary and EOF is reversed. Changes of electroosmotic and electrophoretic mobilities with increasing CPBr concentration were investigated. Under optimum separation conditions, running electrolyte contains 50% MeCN, 20 mM acetate, and 40 mM CPBr at pH = 4.0. Using high concentration of organic solvent, aggregation of surfactants into micelles is prevented. Significant retentions indicate solvophobic, n- and π-electron interactions between CPBr monomers and PAHs.