The aim of the study was to determine the stability and heat resistance of extra premium olive oil. The study material consisted of six extra virgin olive oils (EVOO) obtained from Spain. Four samples were single-strain olive oils: Arbequina, Picual, Manzanilla, and Cornicabra. Two samples were a coupage of Arbequina and Picual varieties: Armonia (70% Arbequina and 30% Picual) and Sensation (70% Picual and 30% Arbequina). Olive oil samples were heated at 170 °C and 200 °C in a pan (thin layer model). In all samples, changes in indexes of lipid nutritional quality (PUFA/SFA, index of atherogenicity, index of thrombogenicity, and hypocholesterolemic/hypercholesterolemic ratio), changes in tocopherol, total polar compounds content, and triacylglycerol polymers were determined. Heating olive oil in a thin layer led to its degradation and depended on the temperature and the type of olive oil. Increasing the temperature from 170 to 200 °C resulted in significantly higher degradation of olive oil. At 200 °C, deterioration of lipid nutritional indices, total tocopherol degradation, and formation of triacylglycerol polymers were observed. A twofold increase in the polar fraction was also observed compared to samples heated at 170 °C. The most stable olive oils were Cornicabra and Picual.