Forty‐five samples of commercial pisco made with Albilla, Muscat and Torontel grapes in different areas of Peru have been evaluated by gas chromatography–olfactometry (GC‐O) and chemical quantitative analysis. The GC‐O study revealed that the Peruvian pisco made of these varieties of grapes has an aroma profile formed by nearly 30 odorants. The odorant 2,3‐pentanedione was detected only in the Albilla sample, producing significant differences. The chemical analysis of the volatiles of these samples showed volatile profiles quite typical of a wine distillate. The Torontel samples (considered the most aromatic variety) were marked by high levels of terpenes and β‐damascenone, the Albilla samples showed the lowest values of terpenes, which may explain their low scores obtained during the sensory analysis, while the Muscat samples showed intermediate levels of this family of compounds and were characterized by high concentrations of benzyl alcohol and β‐phenylethanol. Furthermore, an evaluation of the sensory contribution of terpenes in these piscos was carried out, demonstrating that linalool is the most odour‐active terpene, exceeding its odour threshold in 34 out of 45 piscos analysed. However, the other terpenes should also be considered as important contributors to the aroma of piscos because a certain degree of cooperation between the components of this family has been demonstrated. The quantitative analysis data allowed us to distinguish pisco samples according to their variety and could explain some sensory differences observed depending on the nature of the grapes. Copyright © 2013 John Wiley & Sons, Ltd.