Improving starch-containing materials, whether food, animal feed, high-tech biomaterials, or engineering plastics, is best done by understanding how biosynthetic processes and any subsequent processing control starch structure, and how this structure controls functional properties. Starch structural characterization is central to this. This review examines how information on the three basic levels of the complex multi-scale structure of starch -individual chains, the branching structure of isolated molecules, and the way these molecules form various crystalline and amorphous arrangements -can be obtained from experiment. The techniques include fluorophore-assisted carbohydrate electrophoresis, multipledetector size-exclusion chromatography, and various scattering techniques (light, X-ray, and neutron). Some examples are also given to show how these data provide mechanistic insight into how biosynthetic processes control the structure and how the various structural levels control functional properties.