Thermal isomerization of (all-E)-lycopene and the separation of generated Z-isomers were conducted using a low boiling solvent, dimethyl ether (DME). Because of the low boiling point (-24.8 degrees C), DME is easily separated from lipids and other residues and is extremely low residual. The efficiency of thermal Z-isomerization of (all-E)-lycopene in DME was almost equivalent to using hexane. The thermally generated lycopene Z-isomers were separated by utilizing the solubility differences among lycopene isomers and a characteristic of DME that allows the solubility of compounds to be controlled by changing the temperature. Finally, a lycopene mixture containing 72.0% Z-isomers was obtained from (all-E)-lycopene.