A chiral counter-ion dissolved in the mobile phase can be used to separate enantiomers of acids and amines. The principles and related separation variables have been reviewed. A successful enantiomeric separation is highly dependent on the features of counter-ion chosen for the experiments. The most important properties of a suitable chiral reagent can be summarized as follows: (1) acid-base character of counter-ion; (2) hydrophobicity of counter-ions; (3) presence of suitable functional groups; (4) enantiomeric purity of counter-ion, etc. It is also discussed about the influences of various chromatographic conditions and the applications of chiral ion-pair chromatography.