In order to explore the variation in volatile compounds and aroma profiles of different varieties of sugarcane wine, volatile compounds of 14 different varieties of sugarcane wine were analyzed by headspace solid-phase microextraction–gas chromatography–mass spectrometry (HS-SPME-GC-MS) and an electronic sensory system. The differences in flavor substances of different cultivars of sugarcane were assessed by orthogonal partial least squares discriminant analysis (OPLS-DA) discriminant model and relative odor activity value (ROAV) combined with multivariate statistical methods. The results showed that a total of sixty major volatile compounds, i.e., 27 esters, 15 alcohols, eight acids, three phenols, four aldehydes and ketones, and four others, were identified in 14 types of sugarcane wine. Seven key aroma compounds were screened out: ethyl caprylate, ethyl caprate, ethyl acetate, ethyl laurate, n-decanoic acid, 2,4-di-tert-butylphenol, and 2-phenylethanol and three differential aromas, i.e., ethyl palmitate, isobutyl alcohol, and caprylic acid. The electronic nose and electronic tongue analysis technology can effectively distinguish the aroma and taste of 14 sugarcane wines. It is confirmed that the aroma and taste of 14 sugarcane wines have differences in distribution patterns, and the results are consistent with the analysis and assessment of volatile compounds of sugarcane wine. The results of this study provide technical support for the production and quality improvement of sugarcane wine.
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