To obtain the subject compound useful for medicines or agrochemicals in high optical purity and high yield by adding asymmetric hydrogen in dienol or enynol ester in the presence of a rhodium catalyst.

The objective chiral allylic alcohol ester is obtained by subjecting a dienol ester of formula II (R and R' are each a 1-20C alkyl, a 6-20C aryl, a 4-20C heteroaryl, etc.) or an enynol ester of formula III to hydrogen addition polymerization in the presence of 0.5-1 mol% of a rhodium catalyst, e.g. a rhodium (I) compound of formula I (R" is a 1-4C alkyl) produced from bis(1,5-cyclooctadienyl)rhodium (I) tetrafluoroborate and a chiral bisphosphine ligand and using tetrahydrofuran and methanol as solvents, at from a freezing point to a boiling point of a solvent, preferably 0-65°C under a pressure of 1-100 atm.