NMR spectroscopy is used to study the structure and composition of diverse food materials including starch, which is utilised in food and other industries. NMR spectroscopy has been used to investigate the properties of various starch systems. These include chemical composition, physical and chemical structures, gelatinization, retrogradation, enzyme hydrolysis, and modifications of starches from diverse botanical origins. The interactions of starch with other food components in complex systems have also been studied by NMR spectroscopy. Both solid and liquid state NMR techniques have been used, including 1H NMR, 13C NMR, 31P NMR, and 17O NMR. These techniques can be non-destructive, and provide novel insights into the structure of starch systems. NMR spectroscopy is complementary to other analytical techniques such as X-ray diffraction and calorimetry for the characterization of simple and complex starch systems.