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Cereal starch is a low cost raw material and is widely used in food as well as non-food applications. The structure and properties of starch vary greatly between as well as within species. This offers many possibilities for the industry to find starch with good properties for a wide range of applications. Starch structure and properties have been studied extensively for many years, but we still do not have a good understanding of the link between starch molecular structure and function. The choices of starch material for various applications are thus mostly based on empirical results. Improved methods to describe the amylopectin molecular structure is needed to reveal new factors that influence the properties of this molecule. A novel method focused on the branching pattern of amylopectin has been applied to barley starch and the results have been linked to thermal properties such as gelatinisation and retrogradation. Regression analysis indicates that the branching density locally in the amylopectin molecule is an important factor, especially for retrogradation.