The Mediterranean diet is characterized not only by high consumption of vegetables and fruit, cereal products, legume seeds and olive oil but also by high average consumption of fish, dairy products and wine. Wine is a known and valued product in the Mediterranean tradition because of its health-promoting properties, which are associated mainly with red and dry wines, which are rich in polyphenols. The cardioprotective effects of wine have been shown to inhibit the development of atherosclerosis and cardiovascular diseases. SIR enables the characterization of wine-producing regions and the detection of adulteration. To improve the efficiency of results, the use of a combination of analytical tools such as SIRA with ICP–MS or ICP–AES. This combined methodology makes it possible to achieve a more advanced approach for determining the authenticity/adulteration of wine and its products. The application of multivariate analysis can lead to considerable improvements, resulting in more effective assessment of food authentication and traceability via SIR, mostly in combination with other analytical approaches. The frequently applied multivariate techniques include PCA, FA, CA and HCA, or less frequently LDA, CDA, DA, PLS–DA and PLS. Finally, more advanced and less commonly used chemometric models include SIMCA, QDA, kNN, GLM, SVM and MLP. Owing to this complex methodology, correct assessment of interregional and intervarietal differentiation as well as other parameter variability have been achieved with respect to fraud detection in wine.