On-line coupled multidimensional gas chromatography (DB-5/Lipodex C)/mass spectrometry was used for direct chiral analysis of linalool in 15 essential oils and 16 fruit species. Whereas in a number of commercial essential oils racemic linalool was found, in the corresponding oils prepared in the laboratory enantioselective distribution of linalool was determined. Among the fruits studied, (R)-(−)-linalool dominated in guava, greengage, lulo (Solanum vestissimum), peach and plum. In arctic bramble, mango, yellow passion fruit, raspberry and strawberry the (S)-(+)-enantiomer prevailed. The occurrence of approximately racemic linalool was established in apricot [(enantiomeric excess (ee) 6.0% (R)], mirabelle plum [ee 9.4%(R)], red passion fruit [ee 9.0% (R)] and pineapple [ee 6.6% (R)].