2,2′-Bis(diphenylphosphino)-1,1′-binaphthalene (BINAP), which is a highly versatile ligand in asymmetric catalysis, can be used as a very promising chiral ligand for synthesis of chiral extractants. This paper reports an enantioselective liquid–liquid extraction system containing (S)-BINAP–metal complex as chiral extractant (selector) to separate the enantiomers of 2-fluoro-phenylalanine (FPA). An interfacial reaction model was established for modeling the equilibrium of the system and excellent agreement between the model predictions and the experimental results was observed. Operation conditions were optimized by modeling and a high enantioselectivity (αop) of 3.64 and performance factor (pf) of 0.1998 was achieved under the optimal extraction conditions, involving pH value of 8, selector concentration of 1 mmol·L−1 and FPA concentration of 2 mmol·L−1 at a temperature of 5 °C. The data presented indicates that the model provides a powerful tool for modeling two-phase enantioselective reactive extraction systems, which is important for designing industrial processes.