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[Display omitted] • Interaction of flavor substances in sesame-flavor baijiu was studied firstly. • Volatile change was the reason for the interaction affecting the flavor perception. • Structure and phase ratio affected the volatility of esters. • The interaction prediction model is established firstly to realize rapid judgment. The interaction between 1,3-dimethyltrisulfide and aroma-active compounds in sesame-flavor baijiu was evaluated by Feller's additive model and Odor Activity Value Approach, and the reason for the interaction can promote the release of fruity and caramel aromas of ethyl caproate, ethyl was explored by the Partition Coefficient Approach. The interaction results indicated that 1,3-dimethyltrisulfide caprate and furan-2-ylmethanol. Others showed masking effect. The Partition Coefficient showed that the effect of 1,3-dimethyltrisulfide on the volatility of esters was one of the reasons for the interaction affecting the flavor perception, and the volatility of ethyl esters with longer carbon chains at high phase ratio (PRs) is more likely to be promoted. Besides, the prediction model was initially proposed: y = 2.0112 ln(x) + 0.1461, which indicated that esters with the olfactory threshold lower than 33.80 μg/L are more likely to have positive effects with 1,3-dimethyltrisulfide, the negative effect is more likely to occur conversely. [ABSTRACT FROM AUTHOR]