In this work, the use of a gas chromatography coupled to an ion mobility spectrometer with a tritium source was investigated for the discrimination of virgin olive oils previously sensory assessed (EU Reg. 1227/2016) and characterized by different quality grades (extra virgin, virgin, lampante). The samples were injected by a headspace system and, after the gas chromatographic separation, the ion mobility data coming from the eluted volatiles were processed with various chemometric tools. The preliminary elaboration evidenced a promising capacity to discriminate the samples according to their quality grade. The proposed approach is also sustainable and fast. This work was developed in the context of the project OLEUM “Advanced solutions for assuring authenticity and quality of olive oil at global scale“ funded by the European Commission within the Horizon 2020 Programme (2014–2020, grant agreement no. 635690). The information expressed in this abstract reflects the authors’ views; the EC is not liable for the information contained therein. The authors are grateful to the six sensory panels of the OLEUM consortium for the sensory evaluation of samples.