To obtain optically active α-bromoesters having high optical activity and useful as an intermediate raw material for medicines, agrachemicals, etc., without limiting application range of an ester derivotive used as a substrate.

An ester derivative represented by formula I (R1 and R2 are each independently H, an alkyl, etc.; R3 is an alkoxy, R4 is trimethylsilyl, etc.) is reacted with N-bromooxazolidinones of formula II (* is asymmetric carbon atom) to provide the objective optically active α-bromoesters represented by formula III, e.g. methyl 2-bromo-3-phenylpropionate.