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This study evaluated the structural changes in hemicellulose and cellulose from sunflower seeds before and after roasting at 160°C, 190°C, and 220°C. Sugar composition, molecular weight, Fourier transform infrared spectrometry, thermogravimetric, and NMR analyses were utilized to determine the structural properties of these polysaccharides and detect the volatile compounds. The results showed that roasting destroyed the microstructure of these hemicelluloses and cellulose. Glucose and arabinose of hemicellulose were more easily degraded than other sugars during roasting. The galacturonic acid content increased from 7.8% to 46.66% after roasting. The hemicellulose obtained at 220°C had a backbone of D‐xylose residues with a β‐(1→4)‐linkage. The molecular weight of cellulosic polysaccharides decreased with the increase of roasting temperature. The crystallinity increased from 28.92% to 31.86% revealing that mainly the amorphous regions of cellulosic polysaccharides were destroyed by roasting. After roasting, the volatile compounds of these polysaccharides were rich in furfural, which was produced by caramelization and the Maillard reaction, contributing to the characteristic aroma of roasted sunflower seeds. This study provides some information on the relationship between structural changes of polysaccharides and the formation of flavor during roasting sunflower seeds. [ABSTRACT FROM AUTHOR]