Vegetables contain many vitamins (vitamin A, vitamin C, vitamin E, folic acid), mineral elements (Mg, Zn, P), antioxidants and dietary fibre that are beneficial for health. Adequately chosen reliable analytical methods/techniques combined with chemometric tools are effective for categorizing various vegetables and spices, i.e., roots and tubers, bulbs and stems, pods, edible flowers, fruit, leafy vegetables and salads as well as chili peppers. It has been possible to evaluate the nutritive value of these edible plants with respect to geographical and botanical origin. There are numerous scientific reports worldwide concerning multivariate evaluations of the different multielemental compositions and/or stable isotope ratios of numerous groups of vegetables corresponding to different methods of cultivation. Special attention has been given to newer analytical methods, e.g., IRMS, ICP–MS, ICP–OES, CE–UV, TXRF, LIBS. The analytical data can be transformed using multivariate techniques, e.g., CDA, PLS–DA, PCA, SIMCA, ANN. Owing to such an approach, it has been possible to clearly differentiate conventionally grown vegetables from those that are organically cultivated, verifying their authenticity, etc. Moreover, the combination of both analytical and computational procedures enables traceability of the possible influence of different parameters on the quality of studied products, e.g., with regard to interannual or interseasonal variations, degree of polluted plants within a farming area, culinary/technological processing and others. The validated results make it possible to detect product mislabelling to preserve the brand reputations of original products.