Based on chiral ligand exchange, the distribution behavior of mandelic acid enantiomers in the two-phase system containing copper ion(Ⅱ)(Cu2+) and N-n-dedecane-L-hydroxyproline (L), was studied. At different pH, the partition of Cu2+ in the two-phase system containing N-n-dedecane-L-hydroxyproline, was investigated. The formation constant of binary cpmplex(Li2Cu) was obtained by regression. The influence of pH, concentrations of Cu2+ and chiral ligand, and solvents on partition coefficients(K) and separation factor(α), was discussed. The experimental results show that Li forms more stable ternary complex with D-mandelic acid than with L- mandelic acid. There is a large influence of pH on K and α. At low pH values (<3.5), formation of binary complexes is thermodynamically unfavourable. K and α are best when pH values are above 3.5 and the molar ratio of chiral ligand to Cu2+ is 2:1. At the same time, solvents influence K and α very much.