<jats:title>Abstract</jats:title><jats:p>The elution profiles of several essential oils of the <jats:italic>Myrtaceae</jats:italic> family were acquired using a single enantioselective stationary phase column. These chromatograms were compared with those obtained by using a two‐column coupled system, which comprised a low‐polarity stationary phase column connected to the terminal end of the enantioselective column. The enantiomeric distributions of <jats:italic>β</jats:italic>‐pinene, sabinene, <jats:italic>α</jats:italic>‐phellandrene, limonene, <jats:italic>trans</jats:italic>‐ and <jats:italic>cis</jats:italic>‐sabinene hydrate, linalool, terpinen‐4‐ol and <jats:italic>α</jats:italic>‐terpineol were determined. The use of a two‐column coupled system is demonstrated to be useful for improving the resolution of target (chiral) compounds from otherwise interfering matrix components. Copyright © 2004 John Wiley & Sons, Ltd.