Dataset containing SPME-GC-MS raw analytical data (total ion chromatograms, not aligned) obtained and used by Quintanilla-Casas et al. (LWT - Food Science and Technology 121: 108936). Data correspond to the volatile fingerprint of 174 authentic and traceable virgin olive oil samples previously graded by six official sensory panels (data from 2 outlier samples are not included) in the framework of OLEUM project (EC H2020 Programme 2014–2020). Briefly, data correspond to SPME-GC-MS scan intensities of the total ion chromatogram at each retention time from 5.5 to 61.96 min. These data were aligned and used under a fingerprinting approach by Quintanilla-Casas et al. to develop a classification model (PLS-DA approach) to verify the sensory quality of virgin olive oils, and it was suggested as an instrumental method to support sensory panels.