Enantiometers of D,L-phenylalanine were separated by capillary electrophoresis based on the principle of ligand exchange. Copper (II) complex of 4-hydroxy-L-proline was used as chiral selector. The separation and the migration order of D- and L-phenylalanine were strongly affected by adding an anion surfactant sodium dodecylsulfate (SDS). Without SDS in the electrolyte, the separation was also carried out but the resolution was very small. With SDS added into the electrolyte, the resolution decreased with increasing concentration of SDS until 5.0 mM. When the concentration of SDS in the electrolyte was over 5.0 mM, inversion of the migration order of DL-phenylalanine was observed and the resolution was also increased with increasing concentration up to 20 mM. It was interesting to find that the inversion of the migration order took place not only in the enantioscparation but also in the positional isomers. A family of a fluorinated amino acid, o-, m- and p-fluoro-D,L-phenylalanine was separated and the inversion of the migration order is discussed.