A series of chiral 1,3-dioxolanes, 3-12, with >99% ee values, have been synthesized. This is the first study of chiral ketalization reaction starting from ketones with aryl, monosubstituted aryl, and long alkyl chains (C 11 -AC 13 ). Their ee values were determined by chiral high-performance liquid chromatography (HPLC) on Chiralcel OD column, using their racemic 1,3-dioxolanes rac-3-12, which were also synthesized for the first time. These chiral and racemic 1,3-dioxolanes were characterizated by infrared, NMR ( 1 H, 13 C), mass spectrometry, elemental analysis, optical rotation, and chiral HPLC.