Starch is the most important source of energy for humans, and it is present in many products derived from cereals, legumes and tubers. Interestingly, some of these food products can have different metabolic effects (e.g. change of postprandial blood glucose concentration) although the total amount of starch is the same. This review focuses on a microstructural perspective of the glycemic response, in search of an alternative and complementary explanation of this phenomenon. Several starch and food microstructures are responsible for the change in starch bioaccessibility. Aspects such as the characterization of the microstructure of starchy products and, its relation to the metabolic problem, the crucial role of the food matrix and other components in the ingested meal, and the gaps in our present knowledge are discussed.