The release of aldehydes from aqueous model systems containing starch or maltodextrins with different dextrose‐equivalent (DE) values was evaluated using static headspace analysis. The patterns of aldehydes released differed significantly between starch and maltodextrin solutions with DE values of 4.0–7.0, 13.0–17.0, and 16.5–19.5. The release of most of aldehydes showed an increasing tendency according to DE values of maltodextrins. The release of most aldehydes decreased up to around 24 h, but then increased slightly at 48 h. In addition, the absorbance values of iodine‐polysaccharide complexes and the particle sizes of the polysaccharides were measured to investigate the effects of hydrophobic regions and the intermolecular aggregation of polysaccharides on the releases of aldehydes. The absorbance values of iodine‐polysaccharide complexes, which could be related to the internal hydrophobic regions, decreased in the maltodextrin and starch solutions as the equilibrium time increased up to 24 h, but then increased at 48 h. Also, the particle size increased gradually to 48 h, suggesting that the intermolecular aggregation of polysaccharides affects the release of aldehydes.