The tertiary amine-catalyzed direct asymmetric aldol reac- tion of 2-hydroxyacetophenones (2-hydroxy-1-arylethan- ones) with a variety of aliphatic aldehydes has been demon- strated. By using 20 mol-% of unmodified cinchonine as cata- lyst, the direct aldol reaction products were isolated in good yields and with remarkably high syn diastereocontrol andgood asymmetric induction (40–78% ee ). This newly elabo- rated tertiary-amine-catalyzed direct asymmetric aldol reac- tion has extended the scope of organocatalytic processes to aromatic α -hydroxy ketones, which have hitherto been unre- active towards enamine catalysis.