Abstract Extra virgin olive oils from drupes of three Sicilian varieties (Biancolilla, Cerasuola, and Nocellara del Belice) collected at three different harvesting periods were analyzed upon heating by means of DSC, and thermal properties were related to the chemical composition of the samples. All thermograms exhibited multiple transitions with a minor exothermic peak, followed by a major endothermic event. Cerasuola samples showed higher overall enthalpy and narrower range of transition at all harvesting periods, as compared to the other oils. A more ordered crystal structure originating from a more uniform chemical composition, with higher triolein content, in Cerasuola may be hypothesized. At different harvesting periods, thermal transitions started at lower temperatures and developed over a narrower range in all cultivars, probably due to the insertion of molecules derived from triacylglycerol lysis (diacylglycerols and free fatty acids) and lipid oxidation products into the triacylglycerol crystal lattice. All heating thermograms were deconvoluted into one exothermic and five endothermic constituent peaks, and the effect of chemical components on thermal properties of the peaks was evaluated. DSC application upon heating appears to be very promising in discriminating among oil samples from olives of different cultivars and/or harvesting periods.