Wheat, rice, maize, oats, barley, rye, millet and sorghum are important cereals. A combination of selected analytical methods with multivariate processing is highly reliable in the differentiation of cereal products with respect to their authentication/adulteration, contributing to the determination of food safety. Among the analytical tools, spectrometric methods such as AAS, IRMS, ICP–MS, ICP–OES and LIBS are the most recommended and applied. Multivariate analysis, e.g. PCA, FA, CDA, PLS–DA, ANN and, less frequently, SIMCA, has been frequently used to evaluate cereal products in terms of their degree of differentiation, e.g. geographical origin, variety and culinary/technological processing. Issues that deserve attention include the relationships between cereal cultivars and their nutritional profiles, as well as the differentiation of conventional and organic crops and farming systems. The application of chemometric tools has led to a deeper understanding of the distribution of mineral components in cereals, which is a key feature in the assessment of their authenticity/adulteration. This contributes to preserving the brand reputation of original products, protecting consumers.