A process for producing an optically active compound based on the hydrolysis of an alkenyl ester compound or the cleavage of an alkenyl ether compound. The process uses neither an acidic compound nor a basic compound, and reactants can be reacted in a high concentration. It does not necessitate a buffer, nutrient, etc. unlike enzymatic reactions or reactions using a microorganism. It is a simple process which attains a satisfactory production efficiency. The process, which is for producing an optically active carboxylic acid or optically active alcohol represented by the general formula (VI): (wherein R.sup.1, R.sup.2, and R.sup.3 are different groups; and A represents methylene, carbonyl, or a single bond), is characterized by causing water to act on an alkenyl ester or alkenyl ether represented by the general formula (I): (wherein R.sup.4, R.sup.5, and R.sup.6 each represents hydrogen, alkyl, etc.) in the presence of a specific transition metal complex having an optically active ligand.