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In recent years, the demand for olive oils from the Douro region (Portugal) has increased in line with wine. Thus, it is essential to characterise these olive oils to evaluate them. Therefore, this work describes the sensory and volatile profiles of olive oils produced in the Douro region. These were mainly identified as ripe fruity. Among the olfactory and gustatory sensations, the attributes of dried fruits, tomato, apple, tomato leaves, banana, and lavender stood out. Regarding volatile compounds, the following were detected in all samples: (<i>E</i>)-2-hexenal, (<i>Z</i>)-3-hexen-1-ol, (<i>E</i>)-2-hexen-1-ol, (<i>Z</i>)-3-hexen-1-ol acetate, 1-hexanol, and 2-methyl-4-pentanal. Moreover, it was impossible to separate the olive oils by sub-regions. In conclusion, studying the volatile fraction and their relationship with sensory attributes are essential to guarantee the genuineness and identity of these olive oils with a view to their future appreciation.