The effects of UV radiation on the chemical and sensory characteristics of virgin olive oils (cv. Arbequina and Picual) were assessed. Even small doses of UV radiation induced oxidation of the virgin olive oil samples. Total phenols and fatty acids contents decreased during the process as well as the intensity of the bitter and fruity sensory attributes, while the intensity of the rancid sensory attribute notably increased. Acetaldehyde, 2-butenal, 2-pentenal, octane, octanal, hexanal, nonanal, and 2-decenal were the volatile compounds most affected, showing an important increase during the irradiation process. Nonanal, hexanal, and pentanal showed high correlation with the rancid sensory attribute (90%, 86%, and 86%, respectively). 2-Decenal and nonanal concentrations allowed us to predict the alteration level of the samples by mean of multiple Ridge regression.