Heating deteriorates the physicochemical properties of a vegetable oil for both edible and biofuel uses. The parameters for edible olive oil are established by European Union regulations and by the International Olive Council. The properties of a vegetable oil to be used as a source for biodiesel production are indicated by the German DIN 51605 for rapeseed oil. Biofuel properties are described by the European EN 14214 and the North American ASTM 6751 standards for biodiesel. It is useful to know how temperature and heating duration influence the physicochemical properties of olive oil. Free acidity, refractive index and myristic acid were not significantly influenced by temperature and heating duration. K232, K266, K270, K274, p‐anisidine value, totox index, kinematic viscosity (at 30, 40, 50 °C), estimated higher heating value, relative density, and cetane number increased during olive oil heating. The biological properties: iodine value, oxidative stability index, antiradical (2,2‐diphenyl‐1‐picrylhydrazyl radical, DPPH∙) activity, and phenol content, decreased when time and temperature increased. Fatty acid methyl esters were highly influenced by the applied variables. Almost all the fatty acid methyl esters, except myristic, stearic, and arachidic acid esters, were influenced by the combined effect of temperature and time in a very highly significant level. These results show how temperature and duration of heating influence extra virgin olive oil degradation for both edible use and biodiesel production.