AbstractThe volatile constituents of the lulo fruit (Solanum vestissimum D.) peelings were obtained by liquid–liquid extraction using pentane–dichloromethane mixture (2:1, v/v). In total, 61 components were identified by HRGC and HRGC–MS analysis. Among them, methyl 3‐hydroxyhexanoate, γ‐hexalactone, benzyl alcohol, hexadecanoic acid, (Z)‐hex‐2‐enyl acetate, (E)‐hex‐2‐en‐1‐ol, (Z)‐hex‐3‐en‐1‐ol, (Z)‐isoeugenol, vanillin and 3‐hydroxy‐7‐8‐didehydro‐β‐ionone were found to be the major constituents. Chirospecific MDGC analysis revealed the presence of racemic mixtures each of methyl 3‐hydroxybutanoate, methyl 3‐acetoxybutanoate, and linalol. For ethyl 3‐hydroxybutanoate, methyl 3‐hydroxyhexanoate, and γ‐hexalactone enantiomeric distributions of 28:72%, 16:86%, and 10:90%, each of (S):(R), respectively, were determined.