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There are different ways to classify whole grain carbohydrates (Table 4.1) focusing on different aspects, including chemical structure and complexity as well as nutritional bioavailability (rate, extent and location of digestion/fermentation). While simple monosaccharides can be directly absorbed, they are in very low amount in whole grain foods. The main carbohydrates are starch and non‐starch polysaccharides with highly complex structures (Table 4.2). Their contribution to carbohydrate quality in whole grain foods is the focus of this chapter.