Equilibrium study on enantionselective extraction of 2-chlorophenylglycine (CPG) enantiomers with S-BINAP-metal complexes as selector was performed. A reactive extraction model with an interfacial reaction of CPG enantiomers with S-BINAP-metal complex was established. The extraction system shows good selectivity towards CPG enantiomers. [(S-BINAP)Cu(CH3CN)][PF6] (BINAP-Cu) exhibits the highest selectivity among the selectors studied. Efficiency of the extraction depends, often strongly, on a number of process variables, including types of organic solvents and metal precursors, concentration of the selector, the pH, and the temperature. The model quantitatively predicts extraction performance as a function of key operating parameters, providing a simple computational approach to process optimization. High enantioselectivity of 3.01 was obtained.