Modification of micellar phases with solubilized solutes was examined to control the separation in micellar electrokinetic chromatography (MEKC). The addition of organic hydroxy compounds (1-hexanol, cyclohexanol and phenol) as modifiers to a micellar solution of sodium dodecyl sulfate specifically decreased the capacity factor of some aromatic analytes possessing hydrophilic functional groups. The effect of phenol was different in selectivity to that of 1-hexanol and cyclohexanol. The effects of these modifiers were mainly explained in terms of the saturation of the micellar palisade layer with the modifiers and the hydrogen-bond interaction between the modifier and analyte molecules in the micellar phase. Such micellar modification were applied to improve the MEKC separation.