Olive oil has been characterized by rapid proton transfer reaction-mass spectrometry (PTR-MS) headspace analysis without any concentration of the volatiles or pretreatment of the samples. Comparison of extra virgin and defective (rancid) samples, as described by a panel of sensory judges, and the monitoring of thermo-oxidation processes are discussed. Multivariate analysis of PTR-MS data has been carried out and cross-validated, providing (i) reliable classification models for extra virgin oil as opposed to defective oil and (ii) calibration models able to predict independently thermo-oxidative degradation and the corresponding peroxide value. PTR-MS fragmentation patterns of volatiles considered in this study are also reported.