In this paper, the content of all major carbohydrates and the spatial distribution of starch, arabinoxylan and β-glucan in developing wheat kernels (Triticum aestivum L. var. Homeros) from anthesis until maturity were studied. By combining information from microscopy and quantitative analysis, a comprehensive overview on the changes in storage and structural carbohydrates in developing grains was obtained. In the phase of cell division and expansion, grains were characterized by a rapid accumulation of water and high concentrations of the water soluble carbohydrates fructan, sucrose, glucose and fructose. During the grain filling phase, starch, protein, β-glucan and arabinoxylan accumulated while during grain maturation and desiccation only a loss of moisture took place. The comprehensive approach of this study allowed finding correlations which are discussed within the context of grain development. Particular attention was given to the transient presence of high fructan concentrations, which was associated with the most striking compositional changes during grain development.