The separation of linalool enantiomer was investigated by ultra performance convergence chromatography（UPC2）using β-cyclodextrin as chiral stationary. The influences of different organic modifiers,active back pressure（ABPR）,column temperature and injection volume on separation of linalool enantiomer were studied.The results showed that the acetonitrile as an organic modifier was better than methanol.The retention time and degree of separation were gradually reduced with the column temperature increasing from 30 ℃ to 55 ℃. When the concentration of linalool was 0.01% and injection volume was 3 μL,linalool enantiomers could be successfully separated in 3 min with the best peak shape and good resolution. Therefore,the optimal conditions were as follows:chromatographic column:CAPCELL PAK Chiral CD-Ph（150 mm×3.0 mm,4.6 μm）；mobile phase:CO2-acetonitrile（97∶3）； flow rate:1.2 mL/min；column temperature:30 ℃； injection volume:3 μL；detection wavelength:215 nm；active back pressure（ABPR）:1 700 psi.The thermodynamic mechanism for linalool enantiomeric separation under ultra performance convergence chromatography was preliminarily studied,which could provide the experimental foundation for using UPC2 separated chiral compounds.