AbstractVolatile fractions of rocket (Eruca sativa Mill.) flowers and leaves with green beans were isolated by hydrodistillation in a Clevenger apparatus from fresh plant material prior to and after autolysis and from dried plant material. All isolates of volatile compounds were analysed by gas chromatography/gas chromatography–mass spectrometry (GC/GC–MS). Sulphur and/or nitrogen compounds, fatty acids and esters, aliphatic alcohols and carbonyl compounds and some other compounds in smaller percentages were identified. The main sulphur and/or nitrogen components were glucoerucin degradation volatiles: 4‐methylthiobutyl isothiocyanate (9.0–81.7%) and 5‐methylthiopentanenitrile (2.4–17.7%). Also, fatty acids and esters were identified as major components, such as: decanoic acid (1.2–32.8%), hexadecanoic acid (2.7–22.3%), dodecanoic acid (0.6–8.7%), (E,E)‐9,12‐octadecadienoic acid (6.5%), tetradecanoic acid (1.5–6.4%), methyl linolenate (0.4–5.1%) and methyl hexadecanoate (0.3–1.2%). The O‐glycosides of volatile compounds were isolated from fresh plant material of rocket flowers and leaves with green beans. After the enzymatic hydrolysis of glycosides and analysis by GC and GC–MS, 27 volatile aglycones were identified for the first time. The main aglycones were: 2‐phenylethyl alcohol (23.4–62.8%), methyl vanillate (5.4–12.4%), benzyl alcohol (5.4–8.6%), eugenol (1.2–7.5%), p‐anisyl alcohol (0.4–4.6%), 3‐oxo‐α‐ionol (0.4–3.2%), 4‐oxo‐β‐ionol (3.2%), o‐methoxy phenol (1.1–2.8%), phenol (0.3–2.8%) and trans‐carveol (0.2–2.3%). When compared, only (Z)‐3‐hexen‐1‐ol, 2‐methylbutanoic acid and 2‐phenylacetaldehyde were present in volatiles obtained by hydrodistillation and the volatile O‐aglycone fractions. Copyright © 2008 John Wiley & Sons, Ltd.