Different α-and β-substituted aldehydes have been submitted to the catalytic action of almond oxynitrilase (PaHNL), in order to explore the influence of a stereocenter already present in the substrate on the selectivity of this enzyme. The results indicate that naphthyl and alkoxy substituents in the α-and also in the β-position to the aldehyde group significantly influence the stereochemical outcome of the PaHNL-catalyzed transformation.