Extra virgin olive oil (EVOO) is one of the most abundant oils used in a daily diet of Southern and Coastal European cities with its distinctive sensorial profile and health benefits. Because of its high price, EVOO has become one of the most adulterated foods in the world. The most widely used adulterants are seed and nut oils, lower quality olive oils or old olive oils. Many analytical methodologies have been used to detect adulteration. Selected ion flow tube mass spectrometry (SIFT-MS) is a unique method that measures volatile organic compounds (VOC's) simply, rapidly and sensitively. Soft independent modeling of class analogy (SIMCA) was used to distinguish between EVOO samples based on their volatile contents. This study focused on the measurement of the volatile composition of extra virgin olive oils and determines targeted adulteration. Apparent differentiation was detected between adulterated EVOO and EVOO samples. Interclass distances higher than 3 indicates that samples were significantly different. SIFT-MS is a rapid and accurate technique to determine EVOO adulteration with chemometrics. According to partial least squares regression (PLSR) adulteration levels were clear in most samples. 1-Octanol, 1-penten-3-one, 2-phenylethanol, dodecane, anisole, ethyl nonanoate, isobutanoic acid, ocimene, phenol, toluene were determined as the most discriminant compounds to classify adulteration.