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The centenarian olive trees are part of the historical and cultural heritage of the Côa Valley region where a significant number of these specimens can be found. They have high importance in olive grove heritage; however, their genetic and phenotypic diversity is still poorly studied. Recently, Fourier Transform Infrared (FTIR) spectroscopy start to be widely used in several studies in the food field, becoming a powerful analytical tool for the analysis of edible oils and fats. This technique has numerous advantages, allowing a fast and non-destructive analysis, and requiring minimal sample preparation. In this context, FTIR has been applied to classify and identify different fats, detection of virgin olive oils adulteration, determination of trans fatty acids and evaluation of oil mixtures' composition in foods, all this based on the spectral profiles. Considering that there is a great diversity of centenarian olive trees in which the varieties are unknown, the objective of this work was to use the FTIR technique to identify groups of olive oils with similar chemical characteristics, thus reducing the time and required amount of samples for analysis.