Nuclear magnetic resonance (NMR) spectroscopy is a major tool for the analysis of both chemical and physical properties of starches and starch-containing systems. At the molecular level, high-resolution NMR is the method of choice for defining the degree of branching of starch polysaccharides in solution. In the solid state, NMR is the only method that can be used to quantify the relative amount of double helices and single helices, irrespective of whether they are part of crystalline structures or not. Water is a common feature in starch systems, and NMR relaxation methods provide insight into both local motion and interaction with molecular surfaces. Combinations of high-resolution and relaxation features can also be used to provide descriptions of conformation and chemistry as a function of polymer flexibility. This mobility-resolved spectroscopy approach provides a direct link between molecular and rheological properties in starch-based systems.