Negative aromas such as rancid, fusty, winey‐vinegary and frozen are sensory attributes of defective virgin olive oil recognized by the International Olive Council. Solid phase microextraction‐gas chromatography/mass spectrometery (SPME‐GC/MS) was employed to establish a flavour profile for each defective oil. The potential contribution of the identified compounds to the overall aromas of oil samples was assessed by calculating the ratio relative area/odour threshold in air – Relative Area over Threshold (RAOT). The relevant compounds of each defective sensory attributes were suggested: a series of C7‐C12 unsaturated aldehydes, such as 2, 4‐heptadienal, E‐2‐nonenal and E‐2‐octenal, were found to be responsible for rancidity, Z‐3‐hexenyl acetate and nonanoic acid were related to fusty defects, acetic acid and butyric acid were responsible for winey‐vinegary defects, and limonene was found as a relevant compound in frozen oil. Copyright © 2015 John Wiley & Sons, Ltd.