Heptakis (3-0-acetyl-2, 6-di-0-pentyl)-β-cyclodextrin (Lipodex D), and nickel (II)-bis [3-heptafluorobutanoyl-(lR)-camphorate] respectively are proved to be powerful tools to differentiate chiral l-alken-3-yl esters. From commercially available lavender oils l-octen-3-yl acetate and linalyl acetate are directly stereoanalyzed by multidimensional gas chromatography (MDGC) employing heart-cutting techniques from DB-1701 as the pre column onto the chiral main column. Optical purity control of linalyl acetate from some lavender oils is discussed as an indicator of their natural origin.