The non-conventional hydrolysis of mixtures of diastereoisomeric α-bromo acetals, available in high yields, high diastereomeric excesses, and in large amounts, allows the synthesis and the full characterization of enantiomerically pure (2S)- and (2R)-bromoalkyl aryl ketones. The developed methodology represents the first route to enantiomerically pure 2-bromoalkyl aryl ketones of (2R) and (2S) configurations.