Grains are important sources of carbohydrates in global dietary patterns. The majority of these carbohydrates, especially in refined‐grain products, are digestible. Most carbohydrate digestion takes place in the small intestine where monosaccharides (predominantly glucose) are absorbed, delivering energy to the body. However, a considerable part of the carbohydrates, especially in whole grains, is indigestible dietary fibers. These impact gut motility and transit and are useful substrates for the gut microbiota affecting its composition and quality. For the most part, the profile of digestible and indigestible carbohydrates and their complexity determine the nutritional quality of carbohydrates. Whole grains are more complex than refined grains and are promoted as part of a healthy and sustainable diet mainly because the contribution of indigestible carbohydrates, and their co‐passenger nutrients, is significantly higher. Higher consumption of whole grain is recommended because it is associated with lower incidence of, and mortality from, CVD, type 2 diabetes, and some cancers. This may be due in part to effects on the gut microbiota. Although processing of cereals during milling and food manufacturing is necessary to make them edible, it also offers the opportunity to still further improve the nutritional quality of whole‐grain flours and foods made from them. Changing the composition and availability of grain carbohydrates and phytochemicals during processing may positively affect the gut microbiota and improve health.