Abstract The enantiomers of α‐pinene, β‐pinene and limonene were directly determined in complex matrices by multidimensional gas chromatography using a non‐chiral‐chiral column combination. Essential oils, used for the preparation of perfumes and cosmetics, and commercially available perfumery products were analysed without sample clean‐up. The enantiomeric distribution of the monoterpenes investigated allows a quality control of perfumes, a validation of essential oils as well as a differentiation of their natural or artificial origin.