The International Olive Council (IOC) established that olives must be free of odors, off-flavors, and absent of abnormal ongoing alterations or fermentations. The use of electronic devices could help when classifying defects in a fast, non-destructive, cheap, and environmentally friendly way. For all of that, table olives were evaluated according to IOC regulation in order to classify the defect predominant perceiving (DPP) of the table olives and their intensity. Abnormal fermentation defects of Spanish-style table olives were assessed previously by an IOC-validated tasting panel. ‘Zapateria’, ‘Putrid’, and ‘Butyric’ were the defects found at different concentrations. Different volatile compounds were identified by gas chromatography in altered table olives. The same samples were measured with an electronic nose device (E-nose). E-nose data combined with chemometrics algorithms, such as PCA and PLS-DA, were able to successfully discriminate between healthy and non-healthy table olives, being this last one also separated between the first and second categories. Volatile compounds obtained with gas chromatography could be related to the E-nose measuring and sensory analysis, being capable of matching the different defects with their correspondents’ volatile compounds.