Rye sourdough breads go stale more slowly than wheat breads. To understand the peculiarities of bread staling, rye sourdough bread, wheat bread, and a number of starches were studied using wide-angle X-ray diffraction, nuclear magnetic resonance ((13)C CP MAS NMR, (1)H NMR, (31)P NMR), polarized light microscopy, rheological methods, microcalorimetry, and measurement of water activity. The degree of crystallinity of starch in breads decreased with hydration and baking to 3% and increased during 11 days of storage to 21% in rye sourdough bread and to 26% in wheat bread. (13)C NMR spectra show that the chemical structures of rye and wheat amylopectin and amylose contents are very similar; differences were found in the starch phospholipid fraction characterized by (31)P NMR. The (13)C CP MAS NMR spectra demonstrate that starch in rye sourdough breads crystallize in different forms than in wheat bread. It is proposed that different proportions of water incorporation into the crystalline structure of starch during staling and changes in starch fine structure cause the different rates of staling of rye and wheat bread.