The liquid phase methanol synthesis from CO2 over Cu/ZnO/Al2O3 catalyst was studied in a hydrophobic solvent. The products were collected continuously by liquid-liquid separation. The main operating conditions, the solvent recycling rate, and the separation temperature had appreciable effect on the catalytic performances. The separation factor was estimated from calculating the liquid-liquid equilibrium by the UNIFAC activity coefficient model. Water produced appreciably influence the catalytic activity, and the separation temperature changed water concentration in the recycling solvent.