A RP-HPLC method was developed for the enantiomeric separation of γ-schizandrin enantiomers on chiral column Chiralcel OD-RH(celulose tris(3，5-dimethylphenylcarbamate) coated on a 5 μm silica-gel substrate).Effects of mobile phase composition，flow rate and temperature on the separation of enantiomer were investigated.A baseline separation of γ-schizandrin enantiomers was achieved on a Daicel Chiralcel OD-RH column(150 mm×4.6 mm i.d.，5 μm) with methanol and water(90∶10) as mobile phase at flow rate of 0.5 mL/min.The column temperature was set at 20 ℃ and the detection wavelength was 254 nm，in which R-γ-schizandrin was firstly eluted.The Van-t Hoff plots of the lnk versus 1/T showed a good linearity with their correlation coefficients higher than 0.99.The thermodynamic parameters were calculated.The results indicated that the enantioseparation of γ-schizandrin enantiomers was typically enthalpy driven.The hydrogen bond,π-π and dipole dipole played significant roles in the enantiomeric separation of γ-schizandrin.